Composition and method for retention of solvated compounds and ions

ABSTRACT

Storage stable polyhydroxylated aromatic ether adducts of polyalkylene oxide are described. Reactive compositions are formed by combining an ether adduct with an aldehyde, optionally further adding a phenolic-aldehyde prepolymer. The reactive compositions are cured by removing water, by acidification, or both. The cured compositions sorb solvated compounds from environments containing water. The cured compositions are also useful for pre-loading with compounds that are subsequently released at a controlled rate into environments containing water.

PRIORITY

This application claims the benefit of U.S. Provisional Application Ser.No. 61/660,885, entitled “Composition and Method for Retention ofSolvated Compounds and Ions”, filed Jun. 18, 2012, which application ishereby incorporated by reference in its entirety.

BACKGROUND

A number of compositions and methods have been developed to reduce theconcentration of solvated compounds and ions from liquid water orenvironments containing liquid water. Such compositions and methods aredesirable for use in water remediation applications including sewage orwastewater treatment; removal of leacheates such as excess fertilizers,pesticides, herbicides, or nematicides from groundwater sources,particularly where a high rate of percolation of such compounds isknown; remediation of leacheates from e.g. landfill areas or industrialstreams carrying toxins or other hazardous waste; desalinization ofseawater; treatment of municipal water sources; and the like.

Many conventional water remediation compositions and methods are oflimited use in one or more agricultural and industrial processes wheresuch water remediation is needed. Limitations of conventionaltechnologies include inability to maintain dimensional stability andintegrity during use, compositional instability before or during use,foaming during processing or in use, water solubility (too hydrophilic)or insufficient wettability (too hydrophobic), high viscosity leading todifficulties in processing and/or use, pH sensitivity, and limitedranges of compounds that can be sorbed/retained by the composition dueto inherent chemical incompatibilities. In some cases, the cost of aconventional technology is prohibitive.

Conventional technologies include microorganism-based or plant-basedtreatments; use of impermeable membranes to collect leacheates andrunoff for subsequent treatment at a remote treatment/separationfacility, oxidation lagoon, and the like; use of adsorbents such asactivated carbon, silica, silicates, alumina, and synthetic zeolites andclays to capture compounds; solid phase extraction (affinity-basedchromatographic techniques and materials) using compositions such asalkylated silicas or other functionalized silicas or functionalizedclays, and the like; and combinations of these technologies.

Water holding enhancement and ion exchange capacities in a waterremediation composition are also beneficial but are generally lacking inthe conventional methods and compositions. For example, superabsorbentpolymers (SAP) are useful for water retention in soil, for example, butdue to their hydrophilic or even hygroscopic nature they are nottypically useful for removal of organic compounds from a remediationenvironment. Further, as most SAP rely on ionic groups such aspolyacrylate salts to provide the hygroscopic character of the polymers,the presence of ionic content in the water reduces the ability of theSAP to swell and retain water as compared to the same SAP in asubstantially ion-free environment.

The conventional technologies for water remediation and water retentionare not generally suitable for carrying out the slow and/or controlledrelease of organic compounds. Such release is advantageously employedfor e.g. fertilizers, pesticides, herbicides, or nematicides, whereinthe composition is “preloaded” with a compound, then the preloadedcomposition is applied to soil for release of the compound. Slow releasecompositions are highly desirable in agricultural applications forpreventing leaching out or runoff of the chemicals, where suchcompositions are capable of release of one or more chemicals of interestat a targeted rate. The targeted rate, for example, can be commensuratewith the rate of absorption by a particular plant or group of plants. Insuch cases, the affinity of the composition for the compound to bereleased is key to its release properties. However, most conventionaltechnologies such as those listed above are simply not useful orpracticable for such “reverse” uses as slow and/or controlled release ofchemicals into a selected environment.

One material that is suitable for both water remediation and slowrelease of compounds in agricultural applications is described byElliott, U.S. Pat. No. 6,811,703 (“Elliott”). Elliott teachescompositions and methods related to the reaction of a methylolateddialkyl diphenol with a monoalkyl ether adduct of a polyalkylene oxidebromide to yield a polyalkylene oxide adduct of the methylolated dialkyldiphenol, or polyoxyetheralkyldiphenol. The adduct is then employed in areaction with a phenolic aldehyde prepolymer either in an aqueousenvironment or on a solid support, relying on the methylol moieties ofthe adduct to achieve the reaction with the phenolic aldehydeprepolymer. The compositions can be used directly, or sprayed and curedon a particulate solid support, for water remediation. Once applied tothe remediation environment, the crosslinked network polymer iseffective at reducing and retaining a plethora of organic compounds.Additionally, the crosslinked composition adheres to ion exchangecompositions such as clays, enabling scavenging of ionic entities fromthe remediation environment.

Once the phenolic aldehyde is mixed with the adduct, the crosslinkingreaction takes place at commonly employed storage temperatures (e.g.between 0° C. and 30° C.) leading to a limited shelf life. Because ofthis reactivity, application of the composition to the remediationenvironment, or spraying the composition onto the surface of aparticulate, must be carried out within a few days of mixing the adductwith the prepolymer.

Additionally, a preferred diphenol starting material in the compositionsof Elliott is bisphenol A (4-[2-(4-hydroxyphenyl)propan-2-yl]phenol), asuspected xenoestrogen that has been associated medically withorganizational changes in the prostate, breast, testis, mammary glands,body size, brain structure and chemistry, and behavior of laboratoryanimals. Where bisphenol A is employed, it is methylolated by reactingthe bisphenol with formaldehyde, a known carcinogen. Both bisphenol Aand formaldehyde are considered undesirable compounds in the industryand thus suitable replacements or alternative materials are activelysought.

Smith et al., U.S. Pat. No. 3,857,815 (“Smith”) teaches a polypropyleneglycol or polybutylene glycol modified phenolic aldehyde resole. Resolesare phenol formaldehyde resins having a ratio of formaldehyde to phenolof at least 1 and typically about 1.5. The materials of Smith are formedby blending a phenolic aldehyde with polyalkylene glycol plus aniline orm-hydroxyaniline, then curing with excess formaldehyde. There is noevidence that the polyalkylene glycol undergoes any reaction with theresole, nor would one of skill expect any reaction between thehydroxyl-terminated alkylene glycol and the resole to occur under theconditions set forth by Smith. Rather, it would appear that thepolylkylene glycol is merely an additive that, depending on molecularweight, becomes entangled or entrapped within the resole, analogous to asemi-interpenetrating network. Such formulations are unsuitable for usein water remediation applications. The remediation environment wouldcause the polyalkylene glycol to leach out of the crosslinked resolenetwork. Such leaching provides instability during use in a watercontaining environment.

There is a need for water remediation compositions that areenvironmentally benign; do not require the use of bisphenol A or excessformaldehyde; are effective for retention of a wide variety of organiccompounds, ionic content, or both in environments containing liquidwater; are storage stable in a convenient form, from which the finalproduct can be easily prepared; have water retention properties; arestable in their intended use environment; and can be used for their slowrelease or controlled release properties, for example in timed releaseof chemicals commonly employed in agriculture.

SUMMARY

We have found that aromatic compounds having at least two hydroxylgroups bonded directly on the same aromatic moiety are reacted withpolyalkylene oxide monoethers to yield the corresponding ether adductsof the polyhydroxylated aromatic compounds; and that these ether adductsare reactive with phenolic aldehyde prepolymers to result in crosslinkednetworks useful as water remediation compositions and/or controlledrelease compositions. The polyhydroxylated aromatic compounds useful informing the compositions of the invention do not require methylolationto incur reactivity with the phenolic aldehyde prepolymer; thus, areduction of the amount of formaldehyde employed in forming the networkis realized when compared to similar reaction schemes employingmethylolated adducts of polyalkylene oxides. Additionally, thereactivity of polyhydroxylated aromatic compounds to aldehyde-mediatedcrosslinking is much greater than that of the reactivity ofmonohydroxylated aromatic compounds such as phenol; similarly, thecorresponding ether adducts of polyhydroxylated aromatic compounds aremore reactive to aldehyde-mediated crosslinking than theirmonohydroxylated ether adduct counterparts. The crosslinking reactiondoes not require the use of bisphenol A or other alkyl diphenols,although such alkyl diphenols are optionally employed.

The ether adduct is formed by reacting a polyhydroxylated aromaticcompound with a functionalized polyalkylene oxide (PAO), for example aPAO bromide, tosylate, mesitylate, nosylate, brosylate, or epoxide.Various PAOs and their copolymers and blends are useful in forming theether adducts.

The ether adducts are shelf-stable. The shelf life of the ether adductsis more than a month, or up to one year or even more than one year. Yetwhen blended with a phenolic aldehyde prepolymer to form a reactivecomposition, the ether adducts give rise to rapid crosslinking. Once thereactive composition is formed, the crosslinking reaction proceedswithout the need for additional curing steps, such as heating, to yielda cured composition of the invention. However, drying, acidification,and/or heating is often carried out using any of a number ofconventional techniques, in order to form a commercially useful endproduct as will be described in more detail herein. Where drying and/orheating is carried out, the composition is dried and heated alone, e.g.in film or droplet form; or on a substrate such as a carrier film orparticle.

In embodiments, the cured compositions are water remediationcompositions and/or controlled release compositions.

In an alternative embodiment, a polyhydroxylated aromatic compound ispre-reacted with a methylolated dialkyl diphenol, and the reactionproduct thereof is then reacted with the functionalized PAO. Theresulting diphenol-functional ether adducts are capable of participatingin crosslinking and bonding reactions with phenolic aldehyde prepolymersupon blending and subsequent activation, similarly to the abovedescribed crosslinking and bonding reactions and with similar advantagesof long shelf life prior to blending the diphenol-functional etheradducts with the phenolic aldehyde prepolymers.

In another alternative embodiment, an amount of formaldehyde is reactedwith a polyhydroxylated aromatic compound or a mixture ofpolyhydroxylated aromatic compounds to yield dimers, trimers, and/orhigher oligomers of the polyhydroxylated aromatic compound or mixturethereof via condensation. The oligomers are then reacted withfunctionalized PAO, wherein one or more PAO chains are bonded to theoligomers. The resulting oligomeric ether adducts are capable ofparticipating in crosslinking and bonding reactions with phenolicaldehyde prepolymers upon blending and subsequent activation, similarlyto the above described crosslinking and bonding reactions and withsimilar advantages of long shelf life.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of the recovery from supernatant of four differentpesticides after contacting solutions of the pesticides with eithersilica sand or a composition of the invention.

FIG. 2 is a plot of the recovery from supernatant of four differentpesticides after contacting solutions of the pesticides with eithersilica sand or a composition of the invention.

FIG. 3 is a plot of recovery of five different pesticides from eithersilica sand or a composition of the invention after contacting them withsolutions of the pesticides.

FIG. 4 is a series of ¹³C NMR traces for compositions of the inventionand controls.

FIG. 5 is a ¹³C NMR trace for a composition of the invention and atheoretical ¹³C NMR trace for a compound.

FIG. 6 is a ¹³C NMR trace for two compositions of the invention and atheoretical ¹³C NMR trace for a compound.

FIG. 7 is a ¹³C NMR trace for two compositions of the invention.

DETAILED DESCRIPTION

A. Definitions

For the purposes of this disclosure, the term “polyhydroxylated aromaticcompound” means an aromatic compound having two or more hydroxyl groupssituated on the same aromatic moiety and bonded directly thereto, thatis, the oxygen of the hydroxyl is bonded to a carbon within the aromaticmoiety. In some embodiments, at least two of the hydroxyl groups aresituated such that conjugative interactions activate or facilitateelectron pair donation between them. The definition includes one or moresuch aromatic moieties; that is, multiple polyhydroxylated aromaticmoieties can be bonded together, with conjugation between aromaticmoieties being optional, provided that each aromatic moiety has at leasttwo hydroxyl groups situated on the same aromatic moiety and bondeddirectly thereto. In some embodiments the polyhydroxylated aromaticcompound has one or more additional substituents bonded thereto.

For the purposes of this disclosure, the term “ether adduct” means acompound having the structureX—O—Ywherein X is the residue of a polyhydroxylated aromatic compound, O isoxygen, and Y is a group containing at least 10 polyalkylene oxiderepeat units.

For the purposes of this disclosure, the term “phenolic aldehydeprepolymer” means a partially condensed product of a phenolic compoundor mixture of phenolic compounds, and an aldehyde or mixture ofaldehydes, wherein the phenolic compound or mixture of phenoliccompounds has undergone some amount of polycondensation in the presenceof the aldehyde or mixture of aldehydes, but curing is not complete. Insome embodiments, the phenolic compound or mixture of phenolic compoundsincludes phenol, resorcinol, or a mixture thereof; and the aldehyde isformaldehyde; however, it will be understood that other compositionsthat cure according to the known mechanisms of cure for phenoliccompounds and aldehydes are included in the definition according to theinvention. The phenolic aldehyde prepolymer is, in various embodiments,a solid or is provided as a solution, emulsion, or dispersion in water.

For the purposes of this disclosure, the term “reactive composition”means a mixture of an ether adduct with either a phenolic aldehydeprepolymer or an aldehyde, prior to any substantial subsequentcondensation reaction.

For the purposes of this disclosure, the term “cured composition” meansthe substantially fully condensed reaction product of a reactivecomposition.

For the purposes of this disclosure, the term “composite composition”means a combination of the cured composition plus one or more additionalelements, compounds, compositions, substrates, or combinations thereof,the combination configured to achieve remediation or releaseperformance.

For the purposes of this disclosure, the term “ion exchange material”means any solid phase material capable of an ion-exchange reaction. Suchmaterials include both naturally arising materials and syntheticmaterials.

For the purpose of this disclosure, the term “water remediation” meansremoval of organic, inorganic, or organometallic compounds, ionicspecies, microorganisms (including viruses, bacteria, and fungi),prions, parasites, or various combinations thereof, from a source ofliquid water via adsorption or absorption. The source can besubstantially water itself; water including one or more dissolvedsolutes, such as seawater; or it can be water, optionally including adissolved solute, that is further entrained in or combined with a solidphase material, such as soil, water or a bodily fluid entrapped in asuperabsorbent polymer, or water within a living organism.

For the purpose of this disclosure, the term “water remediationcomposition” means a cured composition in a form that is useful forwater remediation applications. The water remediation composition is insome embodiments a composite composition, such as a blend, a layeredform, or other suitable format. The water remediation composition maycontain a minor or major fraction of the cured composition by weight orvolume.

For the purpose of this disclosure, the term “remediation environment”means a location and the immediate surrounding area wherein a waterremediation composition is situated, will be situated, or is intended tobe situated.

For the purpose of this disclosure, the term “controlled release” meansaddition of organic or ionic compounds or moieties, or a combination ofboth, to a source of liquid water at a predictable rate of addition. Thesource can be substantially water itself, or it can be water entrainedin or combined with a solid phase material. Examples of the latterinclude water in soil, water entrapped in a superabsorbent polymer, andwater within a living organism.

For the purpose of this disclosure, the term “controlled releasecomposition” means a cured composition in a form that is useful forcontrolled release. The controlled release composition is in someembodiments a composite composition, such as a blend, a layered form, orother suitable format. The controlled release composition may contain aminor or major fraction of the cured composition by weight or volume.

For the purpose of this disclosure, the term “release environment” meansa location and the immediate surrounding area wherein a controlledrelease composition is situated, will be situated, or is intended to besituated.

For the purpose of this disclosure, the term “comprising” is inclusiveor open-ended and does not exclude additional unrecited elements,compositional components, or method steps. Accordingly, such term isintended to be synonymous with the words “has”, “have”, “having”,“includes”, “including”, and any derivatives of these words.

B. Reagents and Reactions

The following materials are advantageously employed, in variouscombinations, in the reactions to form the water remediationcompositions of the invention. In general, the reagents are alsoemployed to form the controlled release compositions of the invention,along with one or more compounds for controlled release that are used toimpregnate the composition. One of skill will recognize that thereagents disclosed in this section are not limiting and additionalvariations thereof are also contemplated; and further, the particularreagents selected in any given reaction scheme are varied in type andamount according to the targeted end product and uses thereof that areenvisioned.

1. Polyhydroxylated Aromatic Compounds

A reagent employed in the reactions leading to the compositions of theinvention is a polyhydroxylated aromatic compound. A polyhydroxylatedaromatic compound is an aromatic compound having two or more hydroxylgroups situated on the same aromatic moiety and bonded directly thereto.Preferred polyhydroxylated aromatic compounds have at least two hydroxylgroups situated such that a conjugative interaction facilitates(activates) electron pair donation to an unsubstituted aromatic carbonof the moiety. In various embodiments, one, two, or more aromatic ringsare present in the polyhydroxylated aromatic compound. In someembodiments additional substituents are present on one or more rings ofthe polyhydroxylated aromatic compound. Blends and adducts of thepolyhydroxylated aromatic compounds are also suitably employed in thereactions leading to the ether adducts as that term is defined above.

Polyhydroxylated aromatic compounds include polyhydroxylated benzenes.Useful polyhydroxylated benzene compounds include dihydroxybenzenes andtrihydroxybenzenes. Dihydroxybenzene compounds useful in the reactionsof the present invention include, in embodiments, hydroquinone(1,4-dihydroxybenzene), catechol (1,2-dihydroxybenzene), and resorcinol(1,3-dihydroxybenzene). Trihydroxybenzene compounds useful in thereactions of the present invention include, in embodiments,phloroglucinol (1,3,5-trihydroxybenzene), hydroxyhydroquinone(1,2,4-trihydroxybenzene), and pyrogallol (1,2,3-benzenetriol). In someembodiments, polyhydroxylated adducts of naphthalene are useful in thereactions of the present invention; examples of such compounds include,in embodiments, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene,1,6-dihydroxynaphthalene, 2,3-dihydroxynaphthalene,2,7-dihydroxynaphthalene, and the like.

In some embodiments, other polyhydroxylated aromatic compounds areuseful in the reactions and compositions of the invention.Polyhydroxylated anthracene, phenanthrene, azulene, and the like aresuitably employed in the reactions that form one or more compositions ofthe invention. Additionally, dimers, trimers, and oligomers ofpolyhydroxylated aromatic compounds are useful in the reactions andcompositions of the invention.

In some embodiments the polyhydroxylated aromatic compound, or a blendof polyhydroxylated aromatic compounds, are pre-condensed oroligomerized. For example, the polycondensation reaction commonlyemployed in forming phenolic aldehyde prepolymers is advantageouslyemployed herein to form dimers, trimers, and higher oligomers of thepolyhydroxylated aromatic compound(s). Specifically, a polyhydroxylatedaromatic compound, a combination of two or more polyhydroxylatedcompounds, or a combination of a polyhydroxylated compound and anadditional aromatic compound are combined with an amount of an aldehydethat is selected to provide the desired level of oligomerization, and anacidic or basic catalyst employed under conditions of mild heat, forexample between 50° C. and 100° C., to obtain the condensation productsthereof. In some embodiments, the molar ratio of aldehyde topolyhydroxylated aromatic compound employed to form an oligomer isbetween about 0.0005:1 to 0.8:1, or about 0.001 to 0.6:1, or about 0.1:1to 0.4:1, or about 0.2:1 to 0.3:1. The oligomers thus formed havemultiple reaction sites that are useful in subsequent steps in theformation of the ether adducts and cured compositions of the reaction,as will be readily recognized by one of skill.

Examples of additional aromatic compounds useful in such condensationreactions with one or more polyhydroxylated aromatic compounds includephenol, alkylated phenol, lignosulfonic acid, phenoldisulfonic acid, andother aromatic compounds without limitation, provided that after thecondensation reaction at least some portion of the condensate includespolyhydroxylated aromatic functionality as defined above.

Additionally, other compounds having more than one polyhydroxylatedaromatic moiety present therein are useful in the reactions andcompositions of the invention. In some embodiments one or more of themultiple polyhydroxylated aromatic moieties are conjugated with respectto one another. In other embodiments, the polyhydroxylated aromaticmoieties are not conjugated with respect to one another; some examplesof such compounds include4,4′-((1E)-1-penten-4-yne-1,5-diyl)biscatechol, quercetin(2-(3,4-dihydroxyphenyl)-3,5,7-trihydroxychromen-4-one), myricetin(3,5,7-trihydroxy-2-(3,4,5-trihydroxyphenyl)chromen-4-one), theaflavin(1,8-bis(3-alpha,5,7-trihydroxy-2-alpha-chromanyl)-5H-benzocyclohepten-5-one)and gossypol(7-(8-formyl-1,6,7-trihydroxy-3-methyl-5-propan-2-ylnaphthalen-2-yl)-2,3,8-trihydroxy-6-methyl-4-propan-2-ylnaphthalene-1-carbaldehyde).

In some embodiments, polyhydroxylated aromatic compounds includenaturally occurring oligomeric structures, or oligomeric structures thatare commercially available. Examples of useful oligomeric structuresinclude tannic acid, humic acid, fulvic acid, and Quebracho extracts. Insome embodiments, such oligomers are employed as the polyhydroxylatedaromatic compound; in other embodiments, these oligomers are furthercondensed with an aldehyde, one or more additional polyhydroxylatedaromatic compounds, one or more additional aromatic compounds, or acombination of two or more of these.

In some embodiments additional substituents are present on one or morerings of the polyhydroxylated aromatic compounds. For example one ormore alkyl, ether, aryl, halogen, amino, amido, imino, carbonyl,carboxylate, or other substituents, or a combination of two or morethereof, may be present as substituents on the ring(s) of thepolyhydroxylated aromatic compounds. Any such additional substituentsare preferably electron donating (activating) substituents because insome embodiments electron withdrawing (deactivating) substituents reducethe reactivity of the polyhydroxylated aromatic compound to thecrosslinking reaction with the phenolic aldehyde prepolymer. Ifadditional substituents are present on the ring(s), then preferablyeither conjugative interaction or the inductive effect of thesubstituent facilitates electron pair donation to an aromatic carbonmoiety during the crosslinking reaction. In embodiments, thesubstituents are not so bulky as to restrict the desired reactivitytoward the reactions that are described below. In some embodiments, oneor more substituents is selected to impart additional functionality tothe cured composition, such as surfactancy, ion exchange capacity,compatibility with a targeted environment, or ability to partition atargeted molecule or group of molecules. In some embodiments, theadditional substituent is methyl; representative embodiments includeorcinol (3,5-dihydroxytoluene) and 2,5-dimethyl resorcinol. In someembodiments, the additional substituent is a C₆-C₂₄ linear or branchedalkyl or alkenyl chain, wherein the presence of the hydrocarbon moietyimparts a hydrophobic locus. In some embodiments, an additionalsubstituent is a sulfonate moiety, such as sodium, lithium, or ammoniumsulfonate; or carboxylate, such as sodium, lithium, or ammoniumcarboxylate. Such additional substituents are also present, in someembodiments, on one or more additional aromatic compounds that areemployed in a condensation reaction with one or more polyhydroxylatedaromatic compounds, one or more aldehydes, or both.

Blends of two or more of any of the polyhydroxylated aromatic compoundsdescribed herein are useful in various embodiments of the invention. Theuse of any of the above alone or in combination is not particularlylimited; rather, the selection and use thereof is suitably adjusted toresult in the desired end product useful in one or more applicationsdescribed herein or others that will be envisioned by one of skill.

2. Polyalkylene Oxides

Another reagent employed in the reactions leading to the products of theinvention is a polyalkylene oxide (PAO). In embodiments, the PAO hasstructure 1:

wherein R is a linear, branched, or cyclic alkyl or aralkyl moiety thatis the same or different for each n group. In some embodiments, R hasbetween 1 and 12 carbons. In some embodiments, R has between 2 and 6carbons. In embodiments, R represents a random or block copolymer,terpolymer, or other copolymeric combination of R moieties. Inembodiments, R is —CH₂—CH₂—, —CH(CH₃)—CH₂—, or a mixture thereof in arandom or block conformation. R′ is H, CH₃, or a linear, branched, orcyclic alkyl, aryl, aralkyl, or the like, optionally having one or moreadditional heteroatoms bonded thereto; and n is between about 10 and1000, or about 25 and 750, or about 50 and 500. In some embodiments, R′is not H. In some such embodiments, R′ is methyl. In other suchembodiments, R′ is a linear or branched alkyl chain having from 4 to 18carbon atoms. In some embodiments, all R are —CH₂—CH₂— and n is betweenabout 50 and 200, or about 75 and 150.

In some embodiments, the PAO is a branched structure, for example a PAOhaving the structure 2:

wherein the values of R, R′, and n are each independently as describedabove with the proviso that at least one R′ is H. In some suchembodiments, each occurrence of n is between about 2 and 1000, or about10 and 750, or about 25 and 500; in other embodiments, the total sum ofall n is between about 10 and 5000, or about 25 and 2500, or about 50and 1000.

Additional branched, hyperbranched, or dendritic type PAO structures areenvisioned and lie within the scope of the invention, as will beappreciated by one of skill. In all such embodiments, at least onehydroxyl group attached to an alkyl moiety is present on the PAO; insome such embodiments, the linear or branched PAO has only one hydroxylgroup.

It will be appreciated by the skilled artisan that the nature of thePAO, including the type and ratio of R moieties, number n of repeatunits, and other variables will be optimized for specific end uses andaffect the nature of water remediation or controlled releaseapplications envisioned within the scope of the invention.

3. Ether Adducts of PAO and Polyhydroxylated Aromatic Compounds

Hydroxyl groups attached to the PAO alkyl moiet(ies) provide reactivecenters for functionalization. Functionalized PAO is employed to bondthe PAO to the polyhydroxylated aromatic compound to form the aromaticPAO ether adduct, as will be described in detail below. The aromatic PAOether adduct (“ether adduct”), in turn, is the reactive moiety by whichthe PAO becomes incorporated into the cured compositions of theinvention during the crosslinking reactions that are also described inmore detail below. We have found that hydroxyl-terminated PAO itselfwill not undergo a reaction with phenolic aldehyde prepolymers undercure conditions; that is, the conditions that cause curing of phenolicaldehyde networks do not lead to the formation of covalent bonds betweenphenolic aldehyde prepolymers and PAO (hydroxyl terminated). Under suchconditions the result is, at best, a semi-interpenetrating network wherePAO is untethered but distributed within the phenolic aldehyde network.Untethered PAOs are unsuitable for water remediation or controlledrelease applications because the PAOs are not stable within the networkand can, for example, migrate and leach out of the network duringprocessing, or use, or both.

Further, and without being limited by theory, we believe that covalentbonding of the PAO within the phenolic aldehyde network is necessary forperformance in many of the envisioned applications. We believe theeffective prevention of phase separation between the phenolic aldehydeand PAO provided by covalent bonding between the materials leads to theobserved results in sequestration, and in some cases subsequentcontrolled release, of various compounds. Additionally, In the case of asolute associated with a covalently bound PAO, capture or release of asolute is a function of the partition coefficient of the system. This isdetermined by the equilibrium concentration of solute in the ambientenvironment (mobile phase) and on the polymeric surface. So the specificPAO employed, as well as the bonding of crosslinked polymer matrixthereto, will serve to either capture compounds from a particularenvironment or provide controlled release thereof into the environment.The ability of the compositions of the invention to capture (remediate)or release compounds is also dependent on variables such as, in a waterenvironment, the amount of water and e.g. rate of flow of water (insoil, for example, this is referred to as the percolation rate)solubility of compound in the ambient water or aqueous solution, andrate of diffusion across the surface of the crosslinked matrix.

The aromatic PAO ether adduct is the means by which the PAO iscovalently bound into the polymer network and thus is a necessary aspectof the invention.

A number of different reactions are suitably employed to form thearomatic PAO ether adduct (“ether adduct”). For example, in someembodiments a simple acid catalysis, coupled with addition of heat, issufficient to cause the condensation reaction of two alcohols—here, thepolyhydroxylated aromatic compound and the hydroxyl terminated PAO—toform the corresponding ether. However, in some such embodiments acidcatalyzed condensation results in the formation of unacceptable amountsof symmetrical ether products, e.g. PAO dimer. Further, in someembodiments PAOs are susceptible to cleavage in acidic environments whensubjected to heat. Thus, in some embodiments it is preferable to employreaction conditions that lead to the formation of asymmetrical ethers,more particularly the asymmetrical ether of a PAO and a polyhydroxylatedaromatic compound, wherein deleterious side reactions are avoided.

In some embodiments, an effective means to form an ether bond betweenthe PAO and the polyhydroxylated aromatic compound is described byKaruppannasamy et al., J. Cat. 66, 281-289 (1990), wherein thoria isemployed as a catalyst that is selective for asymmetric aralkyl etherformation.

In some embodiments, Williamson ether synthesis is an effective means toform the ether bond between the PAO and the polyhydroxylated aromaticcompound. Williamson ether synthesis is a known method by whichasymmetric ethers are formed from alkyl bromides and alcohols. In someembodiments, the bromide intermediate for the Williamson ether synthesisis formed by reacting a PAO having an hydroxyl endgroup with phosphorustribromide (PBr₃). The reaction of aliphatic alcohols with PBr₃ is knownto result in the displacement of the hydroxyl group of the alcohol withbromine to yield the alkyl bromide product. A representative example ofPAO bromide formation, followed by Williamson ether synthesis to yieldthe ether adduct is shown below, employing a linear monoether PAO andhydroquinone:

In some embodiments, both the reaction of the PAO to yield the PAObromide intermediate and the subsequent Williamson ether synthesis arecarried out using synthetic techniques generally described by Elliott,U.S. Pat. No. 6,811,703 and elsewhere employing conventional organicchemistry guidelines.

It will be appreciated that several variations of the bromideintermediate synthesis and subsequent ether adduct formation areselected in various embodiments in order to optimize the finalcomposition for a particular application. For example, in someembodiments where two hydroxyls are present on a PAO, a monobromide ordibromide intermediate is formed. In some embodiments where the endproduct is a PAO dibromide, the PAO is selected to undergo twoWilliamson ether syntheses, leading to a diether adduct of the PAO.Similarly, in other embodiments a branched PAO having two or morehydroxyls is selected for one or more bromide intermediate syntheses andone or more ether syntheses. Similarly, in embodiments where thepolyhydroxylated aromatic compound has three hydroxyl groups, onehydroxyl or two hydroxyls are selected for ether adduct formation byreaction with one or two moles of the PAO bromide intermediate per moleof PAO monobromide. More complicated schemes are also envisioned, forexample wherein PAO dibromides, tribromides etc. or mixtures thereof arereacted with polyhydroxylated aromatic compounds having two, three, ormore hydroxyl groups or mixtures thereof. The only limitation in suchvariations is that the aromatic PAO ether adducts formed thereby have atleast one remaining free hydroxyl group bonded directly to one aromaticmoiety in order to effect the subsequent curing reaction with thephenolic aldehyde prepolymer. In all of these embodiments, the compoundor mixture of compounds that results from the Williamson ether synthesissteps are referred to herein as “ether adducts.”

In somewhat more detail regarding the ether adducts, it is important toadjust the stoichiometric ratio of alkyl bromide moieties to aromatichydroxyl moieties such that there is at least one hydroxyl moietyremaining on at least one polyhydroxylated aromatic compoundincorporated within the ether adduct. In some embodiments, thestoichiometric ratio of alkyl bromide moieties to aromatic hydroxylmoieties is adjusted to provide one hydroxyl group per ether adduct; forexample, the exemplary Williamson ether synthesis scheme shown aboveemploys a 1:1 hydroxyl:ether adduct stoichiometric ratio. In otherembodiments where one of the more complicated reaction schemes describedabove is employed—for example, where a PAO dibromide is reacted with twopolyhydroxylated aromatic compounds, more than two hydroxyls are presenton the polyhydroxylated aromatic compound, etc.—the hydroxyl:etheradduct stoichiometric ratio is selected to be less than one or greaterthan one. In all such embodiments, the stoichiometric ratio isadvantageously selected to optimize the final composition for aparticular application or for compatibility in a particular environment.

Further, in some embodiments, it is advantageous to employ an excessmolar amount of the polyhydroxylated aromatic compound to PAO in orderto ensure that the monoether adduct is favored when carrying out theether formation reaction. This is particularly true where thepolyhydroxylated aromatic compound has two hydroxyl groups; anydifunctional ether moieties that form will greatly reduce the reactivityof the adduct to the subsequent reaction wherein the adduct is reactedwith the phenolic aldehyde prepolymer to provide the cured compositionsof the invention. Thus, in some embodiments where the polyhydroxylatedaromatic compound employed to form the ether adduct has two hydroxylgroups, the molar ratio of polyhydroxylated aromatic compound to PAOemployed in the ether adduct forming reaction is greater than 1:1, forexample about 1.1:1 to 10:1, or about 2:1 to 5:1. In some suchembodiments, the unreacted polyhydroxylated aromatic compound issubsequently separated from the ether adduct; in other embodiments, theblend of unreacted polyhydroxylated aromatic compound and ether adductis employed as-is and blended with the phenolic aldehyde prepolymer. Theunreacted polyhydroxylated aromatic compound is reactive with thephenolic aldehyde prepolymer when employed to form the final product.

Epoxy functional PAOs are also useful intermediates by which thearomatic PAO ether adducts are formed. An epoxy PAO is formed, forexample, by the reaction of an hydroxyl-terminated PAO withepichlorohydrin in a two step reaction:

Such a reaction can be accomplished, for example, employing theprocedures outlined in Andrews, et al., U.S. Pat. No. 5,420,312 or otherconventional literature procedures. Another type of epoxy PAO is formed,in embodiments, by reacting one equivalent of a hydroxyl terminated PAOmonoether with one equivalent of a diglycidyl or diepoxy compound in amanner that causes substantially one epoxy moiety to react with one PAOmoiety, leaving the second epoxy moiety available for the subsequentreaction. The epoxy PAOs are then employed in a reaction with apolyhydroxylated aromatic compound, using conventional procedures thattypically employ protic acid catalysis, to yield the correspondingaromatic PAO ether adduct.

It will be appreciated that several variations of the epoxy PAOintermediate synthesis and subsequent ether adduct formation areselected in various embodiments in order to optimize the finalcomposition for a particular application. Many variations, analogous tothe variations on the PAO bromide/Williamson ether synthesis variationsdescribed above, are employed in suitable embodiments to optimize thecomposition. So, for example, epoxidization and ether formation areenvisioned employing a difunctional PAO starting material; othervariations are envisioned and lie within the scope of the invention.

In each such embodiment, reaction of an hydroxyl-terminated PAO iscarried out with the purpose of imparting a PAO terminal group that iseither reactive with a selected polyhydroxylated aromatic compound toform an aromatic PAO ether adduct, or is a suitable leaving group in areaction with a selected polyhydroxylated aromatic compound to form anaromatic PAO ether adduct. Williamson ether synthesis imparts bromide asa leaving group, while the epichlorohydrin addition imparts a reactiveepoxy group. Examples of additional suitable leaving groups include, forexample, tosylate, brosylate, nosylate, triflate, and mesylate. Otherswill be envisioned by the skilled artisan.

As in the Williamson ether synthetic pathway, the proviso remains thatthe aromatic PAO ether adducts formed thereby have at least oneremaining free hydroxyl group bonded directly to one aromatic moiety inorder to effect the subsequent curing reaction with the phenolicaldehyde prepolymer. In all such embodiments, the compound or mixture ofcompounds that results from the epoxy PAO synthesis and subsequentreaction with a polyhydroxylated aromatic compound are also referred toherein as “ether adducts.”

In some embodiments, the aromatic PAO ether adduct is formed in a proticsolvent, such as water or an alcohol. In other embodiments, the aromaticPAO ether adduct is formed in the melt, using no solvent. In still otherembodiments, the aromatic PAO ether adduct is formed using an aproticsolvent to facilitate the reaction. Aprotic solvents are usefullyemployed, for example, to facilitate the reaction to form the aromaticPAO ether adduct while avoiding hydrolysis or alcoholysis, for example,or a leaving group or reaction with a reactive group. Similarly, 100%solids reactions are employed in some embodiments to form the aromaticPAO ether adduct without side reactions attributable to interaction ofthe solvent with a leaving group or reactive group on the PAO terminus.Illustrative examples of useful aprotic solvents include ethers such asdialkyl ethers, dimethoxyethane, diglyme, and higher dialkyl ethyleneglycol ethers, dialkyl propylene glycol ethers, and cyclic ethers suchas tetrahydrofuran; dimethyl formamide, dimethyl sulfoxide, esters suchas ethyl acetate; and ketones such as acetone and methyl ethyl ketone.Preferably, the aprotic solvent is water soluble and/or able toevaporate under conditions subsequently employed in the synthesis of thecured compositions or composite compositions of the invention.

In one alternative composition, a polyhydroxylated aromatic compound ispre-reacted with a methylolated dialkyl diphenol, such as themethylolated dialkyl diphenols described in Elliott, U.S. Pat. No.6,811,703. The reaction product thereof is then reacted with thefunctionalized PAO as described herein. The resultingdiphenol-functional ether adducts are capable of participating incrosslinking and bonding reactions with phenolic aldehyde prepolymers inthe same fashion as the above described ether adducts. Without wishingto be limited by theory, we believe that the methylolated dialkyldiphenols can act as a source of formaldehyde for the addedpolyhydroxylated aromatic compounds, thus consuming the reactivemethylol groups in a rapid reaction that is similar in nature to thereaction that occurs when the polyhydroxylated aromatic compounds arereacted with a phenolic aldehyde prepolymer. This prevents further crosslinking of the methylolated dialkyl diphenols until such time as thephenolic aldehyde prepolymer is added.

This alternative composition has at least two distinct advantages.First, upon subsequent reaction of the methylolated dialkyldiphenol—polyhydroxylated aromatic adducts (“adducts”) with the PAObromide or epoxide, there are multiple hydroxyl groups, for examplebetween 2 and 100, or for example between 3 and 10 hydroxyl groups oneach adduct. This is advantageous with respect to ensuring that theadducts—and thus the PAO—are fully reacted and bonded within thecrosslinked matrix when the phenolic aldehyde prepolymer is introduced.Second, the pre-reacted adduct ensures that no free diphenol or freepolyhydroxylated aromatic compounds are present after the compositionsof the invention are fully crosslinked. Because some diphenols andpolyhydroxylated aromatic compounds are of concern in the environment,or are volatile at manufacturing or use temperatures, or both, it is anadvantage to avoid the possibility of unreacted residues arising fromthe syntheses employed in conjunction with the cured compositions of theinvention.

Other synthetic pathways to form adducts of polyhydroxylated aromaticcompounds and PAOs will be easily envisioned. However, preferredreaction pathways will avoid the formation of electron-withdrawingmoieties bonded to one or more oxygens of the polyhydroxylated aromaticmoieties. Electron-withdrawing moieties tend to reduce the reactivity ofthe remaining free hydroxyl group(s) present on the aromatic moietytoward the curing conditions and reactions necessary to incorporate thePAO into the phenolic aldehyde network. In part for this reason,reaction pathways resulting in ether formation are electronicallyfavorable for the curing step where the PAO is bonded into the phenolicaldehyde network.

In the various available synthetic pathways employed to form the etheradducts, it is of critical importance for many end uses thereof that ahigh degree of reaction is achieved, that is, it is important tominimize the residual amount of unreacted, and thereby untethered, PAOat the end of the ether adduct reaction. This is because in certain enduses, such as soil remediation or certain medical uses, untethered PAOwill tend to leach out of the cured compositions described below when inthe presence of water encountered during use. This in turn leads to lossof the ability of the cured composition to sequester certain chemicals,or provide slow release thereof. Thus, in embodiments, a selected etheradduct forming reaction will achieve at least 75 mol % yield of etheradduct based on the starting amount of PAO. In some embodiments, one ormore selected reactive pathways result in between about 75 mol % and 100mol % formation of ether adduct based on the starting amount of PAO,where 100 mol % reaction means that no unreacted PAO is detectible inthe final reaction product using any commonly employed means ofdetection, including but not limited to H¹ NMR, C¹² NMR, liquidchromatography, gel permeation chromatography, or another means ofdetection commonly employed by those of skill. In embodiments, theWilliamson ether synthesis results in about 90 mol % to 100 mol %formation of ether adduct based on the starting amount of PAO, or about95 mol % to 99.9 mol % formation of ether adduct based on the startingamount of PAO, or about 97 mol % to 99 mol % formation of ether adductbased on the starting amount of PAO.

4. Phenolic-Aldehyde Prepolymers

Another reagent employed in the reactions leading to the products of theinvention is a phenolic-aldehyde prepolymer (“prepolymer”). The phenoliccomponent of the prepolymer includes phenol and various phenol adducts,including bisphenols, as well as polyhydroxylated aromatic compoundssuch as any of those described above. In some embodiments the prepolymeris a phenol-formaldehyde prepolymer or a resorcinol-formaldehydeprepolymer, or a mixed phenol/resorcinol-formaldehyde prepolymer. Inembodiments, the prepolymer is a commercially available waterbaseddispersion including the partial reaction product of a hydroxylatedand/or polyhydroxylated aromatic compound and an aldehyde. In someembodiments, suitable commercially available prepolymers are in adispersed form wherein the phenolic and aldehyde have undergone someamount of a characteristic condensation reaction, but curing is notcomplete. In such form, the prepolymer is relatively stable in the waterdispersion. Since formaldehyde exists predominantly in solution as adynamic equilibrium of methylene glycol oligomers, the concentration ofthe reactive form of any “free” formaldehyde residing in the prepolymerformulation depends on temperature and pH. Suitable commerciallyavailable phenolic aldehyde prepolymers include novalacs, resoles, andblends thereof. In embodiments, a mixture of novalac and resole typedispersions are employed; in other embodiments, a resole type dispersionis employed alone.

Novalacs are available commercially or as prepared in prepolymerdispersions wherein the molar ratio of aldehyde to hydroxylated aromaticcompound is less than one, and wherein curing is accomplished using acidor base catalysis, in some embodiments employing heat, along with theaddition of an aldehyde or a formaldehyde donor such as hexamethylenetetramine. Examples of suitable novalac cure catalysts include oxalicacid, hydrochloride acid, and sulfonic acid. The prepolymer units aremainly linked by methylene and/or ether groups through the methylolationof the hydroxylated aromatic compound by the reactive form of thealdehyde.

Resoles are phenolic aldehyde resins, similarly available commerciallyor as prepared in phenolic aldehyde prepolymer dispersions, and havingan aldehyde to hydroxylated aromatic compound ratio of greater than one(in embodiments around 1.5). The dispersions are cured after dryingusing heat and a base catalyst. Phenol, formaldehyde, water and catalystare mixed in the desired amount and heated, for example to between about50° C. and 100° C. or between about 60° C. and 80° C. to form aprepolymerized dispersion. The prepolymers will crosslink, inembodiments upon heating to around 120° C., to form methylene anddibenzyl ether bridges via elimination of both the water of dispersionand the water formed by the polycondensation reaction. The result is astable, three-dimensional cured network. The final crosslinking stepgives this type of phenolic resin its characteristic hardness, goodthermal stability, and chemical imperviousness.

Resorcinol resins, or resorcinol-phenol resins, are similar to phenolformaldehyde resins except that resorcinol (benzene-1,3-diol) isemployed in place of, or in combination with, phenol. In embodiments,phenol and resorcinol based resins are employed in conjunction with thecompositions of the invention. Where the recitation herein refers tophenolic aldehyde prepolymers, dispersions, crosslinked compositions,etc. it will be understood that resorcinol or resorcinol-phenol typeresins are additionally referred to and included.

Other phenolic aldehyde prepolymers are within the scope of theinvention and are useful in conjunction with the ether adducts describedabove to form the compositions of the invention. For example, in someembodiments lignin adducts or other aromatic hydroxylated compounds areuseful alone or in mixtures with phenol, resorcinol, or mixtures thereofor as a replacement for phenol or resorcinol in a prepolymer along withformaldehyde. In some embodiments, an aldehyde other than formaldehydeis useful in the phenolic aldehyde prepolymers. For example,acetaldehyde, propionaldehyde, furfuraldehyde, or another aldehyde ormixture of one or more such aldehydes is useful alone or in a mixturewith formaldehyde in the phenolic aldehyde prepolymers. It will beunderstood by one of skill that the term “phenolic aldehyde” means allof these embodiments and combinations thereof.

Examples of suitable waterbased phenolic aldehyde dispersions that areuseful in forming the compositions of the invention include thoseavailable from Momentive™ Performance Materials, LLC of Columbus, Ohiounder the trade names CELLOBOND® and CASCOPHEN®. Examples of suchdispersions include CASCOPHEN® OS 707M, CASCOPHEN® ECO LPF 52,CASCOPHEN® LPF 55, CASCOPHEN® RS 254A and CASCOPHEN® 254D. Anotheruseful dispersion is BINDEX® Resin 73, available from the IndspecChemical Corporation of Petrolia, Pa. Other suitable dispersions areavailable from the Georgia-Pacific Corporation of Atlanta, Ga. and thePlastics Engineering Company, Inc. (“Plenco”) of Sheboygan, Wis. Inembodiments, suitable waterbased phenolic aldehyde dispersions that areuseful in forming the compositions of the invention are between about 40wgt % and 65 wgt % solids, for example about 45 wgt % to 60 wgt %solids. In some embodiments, suitable waterbased phenolic aldehydedispersions that are useful in forming the compositions of the inventionhave viscosity of about 50 cP to 500 cP, or about 75 cP to 300 cP;however, for other applications it may be advantageous to employ adispersion of higher or lower viscosity, depending on the selectedmanufacturing method. While the pH of the dispersions differs dependingon the type of prepolymer and cure catalyst employed, in someembodiments the pH of the dispersion is between 8 and 11 or between 9and 11.

In some embodiments, depending on the end use intended, a high solids oreven a melt-processable phenolic aldehyde resin is useful, wherein thepercent solids is, in some embodiments, between 65 wgt % and 100 wgt %.The viscosity of high solids dispersions is, in some embodiments, inexcess of 500 cP, for example 10 poise to 10,000 poise or more. Meltprocessable compositions (essentially 100% solids) have viscosities thatdepend on the prepolymer molecular weight and processing temperatureemployed. The compositions of the invention are not particularly limitedby the percent solids, viscosity, or molecular weight of the phenolicaldehyde prepolymers employed therein.

In some embodiments, one or more fillers or adjuvant materials arefurther included in the commercial phenolic aldehyde prepolymerdispersions. For example, wood flour, minerals or glass materials, glassfibers, thermoplastic fibers such as nylon or polyester fibers, or othermaterials are present in some useful commercial phenolic aldehyderesins. In some embodiments, as is described more fully below, one ormore ion exchange entities are added to the reactive composition priorto drying and heating, wherein the cured compositions become adhesivelybonded to the ion exchange entities and provide unique performanceattributes for water remediation applications. In other embodiments,fillers or adjuvants are added to the cured compositions. The fillersand adjuvants are, in some embodiments, reinforcing; that is, theyincrease the tensile or compressive strength, impact resistance,modulus, or other physical properties of the compositions of theinvention when the compositions are in fully cured form.

5. Reactive Compositions

In some embodiments, a resole or resole/novalac prepolymer is admixedwith the ether adduct to yield a reactive composition. In forming suchreactive compositions, blending ratios of the prepolymers with the etheradducts are dictated by the total percent solids present in theprepolymer dispersion, if a dispersion is employed, and the type andratio of PAO functionality present in the ether adduct, further in lightof the desired amount of PAO functionality for the end use application.Blending in a dispersion format is typically carried out usingconventional techniques, such as vortex mixing, shaking, or staticmixing. Extrusion mixing is employed in some embodiments for higherviscosity coating compositions or blending of 100% solids compositions.In some embodiments the reactive compositions undergo a minor amount ofreaction while in dispersion form, but such reactions do not cause thedispersion to become unstable, fully cure, precipitate, or phaseseparate. In some embodiments, the reactive compositions containadditional materials such as the fillers and adjuvants described above.In other embodiments, the reactive compositions consist essentially ofan ether adduct, a phenolic aldehyde prepolymer, an amount of a curecatalyst, and water.

In embodiments, a desirable ratio of ether adduct to phenolic aldehydein a reactive composition results in a ratio of theoretical (before anyreaction) phenol or resorcinol groups to formaldehyde of 1:1. Under suchconditions, the phenolic aldehyde becomes completely cured. This isbecause one mole of formaldehyde methylolates one mole of phenol, andmethylolated phenols self-condense. In this sense, a methylolated phenolcan be considered a “reactive hydroxyl” moiety within the system. Theether adducts, when added to the phenolic aldehyde prepolymerdispersion, contribute one or more reactive aromatic loci, in a mannersimilar to phenols that react with methylolated phenols at the 2- or4-locus relative to the single hydroxyl moiety present thereon. Withoutbeing bound by theory, we believe that the ether adducts form methylenebridges with neighboring methylolated phenols in the cured compositions,as will be appreciated by one of skill in the art of phenolic aldehydecuring mechanisms.

While the ether adducts participate in the curing reaction upon contactwith the phenolic aldehyde prepolymer, the inherent difference inreactivity between a methylolated phenol and the activated aromatic locipresent on the ether adducts is the key to the shelf stability of theether adducts. The activated aromatic loci of the ether adducts do notself-condense as do methylolated adducts such as methylolated alkyldiphenols; the ether adducts are therefore shelf-stable for anindefinite period and yet react rapidly when added to a phenolicaldehyde prepolymer. Cure rate of the reactive composition is dependenton temperature. In general, the rate of cure is adjusted according tothe means of application of the reactive composition to a substrate andthe manufacturing considerations that make crosslinking reactionpracticable and result in a product that is useful for the intended enduse.

In contrast to the lack of self-condensation reactivity of the etheradducts noted above, when contacted with formaldehyde, phenolic aldehydeprepolymer, or a combination thereof, the ether adducts of the inventionare more reactive than their monohydroxylated aromatic relatives. Forexample, resorcinol reacts with formaldehyde at a rate that is more than12 times the comparative rate of reaction of formaldehyde with phenol atpH 3.5. (Durairaj, R., Resorcinol Chemistry, Technology, andApplications, ©2005, Springer-Verlag Berlin, Heidelberg, at p. 181.)This rate difference is the minimal difference; the reactivitydifference increases between pH 3.5 and pH of about 11. The differenceis attributable to the enhanced electron density at the benzene ring 2,4, and 6 positions. Thus, ether adducts having resorcinol as a startingmaterial are more reactive in the reactive compositions than phenol oreven phenol derivatives such as m-cresol.

In some embodiments, the ratio of ether adduct to phenolic aldehydeprepolymer employed to form a reactive composition of the invention isadjusted to reflect the intended end use as well as the type and amountof PAO incorporated into the ether adduct. Additionally, as is discussedabove, in some embodiments the ether adducts are formed using an excessmolar ratio of polyhydroxylated aromatic compound; in such embodiments,if the product ether adduct is not separated from the unreactedpolyhydroxylated aromatic compound, the reactive composition is formedusing a mixture of the polyhydroxylated aromatic compound and the etheradduct. In such embodiments the ratio of reacted to unreactedpolyhydroxylated aromatic compound must be accounted for in formulatingthe reactive composition.

In some embodiments, the ratio of ether adduct (including the blends ofether adduct and unreacted polyhydroxylated aromatic compound describedabove) to phenolic aldehyde in the reactive composition is about 5:1 to1:10 by weight of solids, or about 2:1 to 1:7 by weight of solids, orabout 1:1 to 1:5 by weight of solids, or about 1.2:1 to 1:3 by weight ofsolids. Additional components of a reactive composition include, in someembodiments, formaldehyde, water or an aprotic solvent, and a curecatalyst such as sodium hydroxide, sulfuric acid, or a cure catalystresin sold by Georgia Pacific Corporation of Atlanta, Ga. under thetrade name REST-CAT®, such as GP® 012G23 RESI-CAT®. In some embodiments,additional components are employed; such additional components aretypically added in light of a particular end use or end form of thecompositions upon curing. For example, one or more colorants, bleaches,surfactants, solvents, fillers, functional compounds, functionalmaterials such as clay or zeolite, antifungal or antibacterialmaterials, thermal stabilizers, UV stabilizers, and the like areoptionally added to the reactive compositions of the invention so as toprovide a particular composition upon curing.

In some embodiments, reactive compositions that are dispersions have atotal solids content of about 2 to 90 wgt % based on the weight of thedispersion, or about 10 to 80 wgt %, or about 20 to 75 wgt %, or about25 to 60 wgt % solids based on the weight of the dispersion.

In one embodiment, a surfactant is employed in the reactive compositionsof the invention so as to form a stabilized emulsion that remains stableduring and after cure. In some embodiments, the amount and type ofsurfactant employed is optimized for the intended end use and further inlight of the critical micelle concentration of the surfactant, size ofemulsion particles formed at a particular concentration of surfactant,and the like. In some embodiments, formation of an emulsion is notnecessary to stabilize the reactive composition, but rather to maintainemulsion stability during the reaction of the reactive composition, andprovide a cured composition (wherein “cured composition” is described inmore detail below) that is a stable waterbased emulsion. In someembodiments, the surfactant employed is nonionic. In some embodiments,the surfactant employed is ionic. In some embodiments, a mixture of twoor more surfactants and/or surfactant types is employed. In someembodiments, the surfactant is a quaternary amine or ammonium functionalsurfactant, or a phosphatidyl functional surfactant.

In some embodiments, one or more reactive compounds are added to thereactive composition. The reactive compounds are reactive with thereactive compositions of the invention to become bonded into the curedcomposition and in some embodiments undergo the bonding reaction duringthe curing reaction to form the cured composition. In other embodimentsthe reactive compounds are reacted with the cured composition, or arereacted within and/or on the surface of the cured composition. Suchreactive compounds are included in the reactive compositions to addspecific functionality to the cured composition. One example of areactive compound is 3-chloro-2-hydroxypropyltrimethylammonium chloride,sold as a 65 wt % or 69 wt % aqueous solution under the trade name QUAT®188 by the Dow Chemical Co. of Midland, Mich.; inclusion of thiscompound in the reactive composition results in formation of cationicfunctionality within, and in embodiments bonded to, the curedcomposition. In another embodiment, a primary dibromoalkyl compound isreacted with a ternary amine, a phenol, polyhydroxylated aromaticcompound, or ether adduct moiety thus generating a quaternary ammoniumcompound that is prereacted in a manner that will result in itsincorporation into the crosslinked network formed on curing the reactivecompositions of the invention. In some embodiments, a surfactant is areactive compound; in some embodiments, a reactive compound is notitself a surfactant but provides surfactant-like properties once bondedto the cured composition by maintaining the cured composition in anemulsified state after cure. Other chemical functionality is similarlyincorporated in the reactive compositions of the invention with ease.

In some embodiments, a reactive composition is formed by addingformaldehyde or another aldehyde alone to an ether adduct; that is, analdehyde and the ether adduct are reacted without addition of a phenolicaldehyde prepolymer. In such embodiments, the ratio of ether adduct toaldehyde employed to form a reactive composition of the invention isadjusted to reflect the intended end use as well as the type and amountof PAO incorporated into the ether adduct. Additionally, as is discussedabove, in some embodiments the ether adducts are formed using an excessmolar ratio of polyhydroxylated aromatic compound; in such embodiments,if the product ether adduct is not separated from the unreactedpolyhydroxylated aromatic compound, the reactive composition is formedwith an aldehyde and a mixture of the polyhydroxylated aromatic compoundand the ether adduct. In some embodiments, the ratio of ether adduct(including the blends of ether adduct and unreacted polyhydroxylatedaromatic compound described above) to aldehyde in the reactivecomposition is about 5:1 to 1:3 by weight of solids, or about 3:1 to 1:1by weight of solids. Additional components of such reactive compositionsinclude a cure catalyst, such as any of those listed above. In someembodiments, additional components such as any of those listed above arealso included in the reactive composition; further, one or moresurfactants or reactive compounds are suitably employed in the reactivecomposition as described above to impart selected functionality to thereactive composition formed with an aldehyde, further in the absence ofphenolic aldehyde prepolymer.

6. Cured Compositions

The final curing step of the reactive compositions of the invention arecarried out using processes and conditions that are conventionallyemployed to cure commercially available resole type phenolic aldehydeprepolymer dispersions: namely, drying and application of heat; in someembodiments curing includes acidification of the reactive composition.Such conditions are sufficient to cause the ether adducts in thereactive composition to become fully reacted with, and incorporatedinto, the three-dimensional phenolic aldehyde network thus formed. Thecured phenolic aldehyde polymers having ether adducts incorporated andcovalently bonded therein are “cured compositions” of the invention.

Without being limited to theory, we believe that the ether adduct (thatis, the aromatic PAO ether adduct) does not require methylol groups toparticipate in crosslinking with the phenolic aldehyde prepolymer. Thatis, the presence of the methylol groups in the phenol formaldehydeprepolymer is sufficient to cause reactions with the ether adduct,likely at the electronically activated sites on the aromatic ring asdiscussed above, to yield a crosslinked network. It is generally known,in an analogous example, that di- or trihydroxybenzene has a greaterpropensity to spontaneously cross link within a methylolated phenolicprepolymer than e.g. a phenol or diphenol compound, wherein only oneoxygen atom is bonded to a conjugated aromatic compound. Similarly,other fully conjugated aromatic compounds having two or more hydroxylgroups situated in positions that provide an activating amount ofelectron density to one or more unsubstituted loci of the aromaticcompound are suitably employed in the reactions of the invention andlead to reactive compositions having the characteristics of extendedshelf life and no requirement of additional methylol functionality toaccomplish the crosslinking reaction. When such compounds furthercontain PAO substituents, the PAO is thereby incorporated into the curedcompositions of the invention.

In some embodiments, a suitable curing process includes lowering the pHby addition of an acid cure catalyst to the reactive composition. Insome such embodiments, lowering the pH is accomplished along withheating the reactive composition to affect rapid cure. Useful examplesof acid catalysts include any of the known acid catalysts employed tocure conventional phenolic aldehyde polymers, for example sulfuric acid,phosphoric acid, toluenesulfonic acid, phenoldisulfonic acid,phenolsulfonic acid, and cure catalyst resins (solid stateacid-functional resins) such as those sold by Georgia PacificCorporation of Atlanta, Ga. under the trade name RESI-CAT®, such as GP®012G23 RESI-CAT®. In such embodiments, all the components of thereactive composition must be acid stable; thus, in embodiments wheree.g. a surfactant is employed to form an emulsion, the surfactant mustbe stable to acidic components and at the pH employed to acceleratecuring of the reactive composition. The pH of the resulting reactivecomposition is targeted to be 3 or less, ideally between 3 and lessthan 1. In some embodiments, a period of acidic pH is followed byneutralization to a pH of over 3, for example between 3 and 11.5, orbetween 4 and 10 or between 4.5 and 9. Such neutralization minimizesside reactions such as cleavage of the aromatic PAO ether adducts.

In some embodiments, processing of the reactive composition isconcomitant with the curing reaction to yield the final curedcomposition. For example, in some embodiments, coating of the reactivecomposition onto a substrate, drying the coated substrate, and heatingthe substrate to a suitable cure temperature results in formation of thecured composition in situ. In some embodiments, drying is accelerated byheating, for example by forcing dry air into and around the substrateand the like. In such curing processes, suitable coating weights will bedetermined by the percent solids of the reactive composition dispersionand the desired final amount of cured composition when coated on asubstrate. In other embodiments, the reactive compositions are cured inan emulsified form prior to application of the cured composition to afilm, particle, or other surface.

Depending on the cured vs. reactive nature of the composition, percentsolids in water, rate of cure if applicable, intended end use, andsubstrate employed, the amount of the reactive composition or curedemulsified composition coated vary over a broad range of both wet anddry coated weight. The invention is not particularly limited by theamount of material coated as a weight percent of the substrate ontowhich the material is coated. However, examples of suitable coatingweights of the reactive compositions or the cured emulsifiedcompositions of the invention range from about 0.01 to 100 wgt % of thebased on the weight of the substrate, for example about 0.1 to 90 wgt %,or about 0.25 to 80%, or about 0.5 to 60 wgt %, or about 1 to 50 wgt %,or about 5 to 40 wgt %, or about 5 to 30 wgt %, or about 5 to 20 wgt %of the dispersion based on the weight of the substrate. After thecompositions are fully cured and dried, a coated substrate typically hasabout 0.1 to 50 wgt % of the cured composition based on the weight ofthe uncoated substrate; or about 1 to 40 wgt %, or about 2 to 30 wgt %,or about 2 to 20 wgt % cured composition based on the weight of theuncoated substrate.

In the case of porous or absorptive substrates, in some embodiments ahigher amount of both reactive composition and cured emulsifiedcomposition can be added compared to nonporous and nonabsorptivesubstrates. This in turn results in a higher dry weight of curedcomposition to the substrate. For example, an absorptive substrate suchas cotton batting, a superabsorptive polymer, a nonwoven cellulosicsubstrate, and the like could easily take on about 100 to 1000 wgt % ormore of a reactive composition or cured emulsified composition based onthe dry weight of the substrate, or about 200 to 700 wgt % or about 300to 500 wgt % of the reactive composition or cured emulsified compositionbased on the dry weight of the substrate. Depending on the percentsolids in the reactive composition or cured emulsified composition, theadded weight percent solids of the dried cured composition on anabsorptive or porous substrate is in some embodiments as high as 5 to500 wgt % solids added to the substrate based on the weight of theuncoated substrate, although less can be added as selected for theintended end use.

Suitable temperatures employed to cure the reactive composition rangefrom about 30° C. to 200° C., or about 50° C. to 175° C., or about 60°C. to 150° C., or about 100° C. to 150° C., or about 125° C. to 150° C.In some embodiments, the reactive compositions are fully cured afterabout 30 minutes at about 130° C.

In some embodiments, the reactive compositions are fully cured inemulsion form, wherein the cured compositions are stable curedemulsified particles dispersed in water. In some such embodiments, thecured compositions are employed as a spray or a coating that can beapplied by brush, roller, die, or other coating means employed to coatconventional emulsion type products. The stabilized emulsions describedabove are advantageously employed in this manner in some embodiments. Insome embodiments, where a surfactant is bonded to the emulsifiedparticles before or during the curing step, stabilized formulations areformed upon cure wherein the surfactant does not later leach out of theemulsion particles. Where the surfactant is a cationic surfactant, forexample, the cured compositions with surfactant covalently bondedthereto are useful to e.g. bind to cation exchange sites present on asoil or leaf surface.

In some embodiments, a cationic or anionic functionality that isprovided within the cured compositions of the invention impartsurfactancy to the composition, even though the ionic moiety itself isnot a surfactant. In other words, simply providing ionic functionalityto the cured composition causes surfactancy in some embodiments becauseof the PEG chains also present within the cured composition, or thearomatic functionality present, or both; additional functionalityprovided to the cured compositions, such as e.g. C₆-C₂₄ chain alkylgroups as discussed above, are also the source of surfactancy impartedto the cured compositions of the invention.

In some such embodiments the cured composition is employed as a carrierto control the release of an active ingredient and reduce the rate ofleaching of the polymeric carrier; in other embodiments the bindingability of the cured composition is useful for keeping the curedcomposition in its intended location, and/or for increasingcompatibility of a compound to be scavenged by the cured compositions.In other embodiments where a surfactant is included with the reactivecomposition, it is desirable to remove the surfactant after cure, suchas by leaching or washing from the cured composition particles, prior toemploying the cured composition in its intended application.

In a non-limiting example employing a surfactant, a reactive compositionis formed by charging an ether adduct and a phenolic aldehyde prepolymerdispersion in water into a high shear mixer. In some embodiments,additional water is added. In some embodiments, a reactive surfactantwas previously added to the prepolymer; in other embodiments, thesurfactant is added under high shear to facilitate the formation ofmicelles. Under high shear mixing the pH is gradually lowered by theaddition of an acid. Shear is maintained for time sufficient to completethe polymerization and crosslinking of the micelles. In some cases, thetemperature of the dispersion or emulsion is raised to increase the rateof polymerization and cure. In some cases, the final product is filteredto remove oversize coagulum.

In some embodiments, the cured compositions are formed by the reactionof one or more ether adducts and one or more aldehydes, without theinclusion of a phenolic aldehyde prepolymer. In such reactivecompositions, the ether adduct or mixture thereof reacts with thealdehyde or mixture thereof directly in a polycondensation reactioncatalyzed by acid, base, and/or heat to result in a cured composition.For example, the initial reaction of an ether adduct with formaldehydeforms methylol groups on the one or more ether adducts in the reactivecomposition. The alkylol groups self-condense under reactive conditionsto form a cured composition that is a gel-like material.Resorcinol-formaldehyde aerogels were previously reported by Pekala, R.W., J. Mat. Sci. 24 (1989) 3221-3227. The gels of the invention includePAO functionality covalently bound within the gel network. Such gelsinclude, in embodiments, PAO content of 50% by weight of solids or more,for example about 50 wt % to 98 wt % PAO based on total solids; or about75 wt % to 96 wt % PAO based on total solids, or about 90 wt % to 95 wt% PAO based on total solids of the gel. In an additional relatedembodiment, an additional amount of one or more polyhydroxylatedaromatic compounds or additional aromatic compounds are added to thereactive composition and thus incorporated into the cured compositionsof the invention. In some such embodiments, the additional amount of oneor more polyhydroxylated aromatic compounds or additional aromaticcompounds is a compound that includes surfactant-like properties orimparts surfactant-like properties to the cured composition. In one suchrepresentative example, sodium phenoldisulfonate is the additionalaromatic compound. In still another related embodiment, one or moresurfactants are incorporated into the reactive composition and thus arephysically entrained in the gel.

In an embodiment, the gel-like cured compositions are further processedafter formation. In some such embodiments, the gel-like curedcompositions are mechanically disrupted by high shear mixing, forexample by a homogenizer, an ultrasound device, or some other mixingdevice that breaks the gel-like material into colloid-like particulatedispersions in water.

In some embodiments, the gel-like cured compositions or the colloid-likeparticulates are further functionalized to impart a targeted zetapotential to the particle surfaces. For example, in some embodiments,one or more reactive compounds are added to the gel-like curedcomposition either before or after mechanical disruption, wherein thereactive compounds become covalently bound to the cured gel-likecomposition or the colloid-like particulate through reaction withhydroxyl groups residing on the aromatic moieties of the curedcomposition. One example of a reactive compound is3-chloro-2-hydroxypropyltrimethylammonium chloride, sold as a 65 wt % or69 wt % aqueous solution under the trade name QUAT® 188 by the DowChemical Co. of Midland, Mich.; addition of this compound to the curedgel-like composition, or the colloid-like particulate, results information of cationic functionality bonded to the cured composition dueto reactivity of residual nucleophilically activated sites present inthe polyhydroxylated aromatic functionality within the curedcomposition.

Using similar techniques, other chemical functionalities are easilyenvisioned as being incorporated within and bonded to the cured gel-likecompositions or colloid-like particulates of the invention with ease byemploying other reactive compounds. In some embodiments, it isadvantageous to add the selected reactive compound to the curedcomposition rather than the reactive composition, for example where thereactivity of a polyhydroxylated aromatic ring towards cure is decreasedby the presence of the selected functionality once bonded to thepolyhydroxylated aromatic ring.

7. Composite Compositions

In some embodiments of the invention, cured compositions employed aswater remediation compositions, water retention compositions, controlledrelease compositions, and the like are one element of a compositecomposition, wherein the properties of the cured composition works inconjunction with other elements in a composite composition to achievethe remediation or release performance. The other elements of thecomposite composition are, in various embodiments, one or morecompounds, polymers, particles, substrates including films, fibers,adjuvants, fillers, and combinations of two or more thereof. Theelements are used in conjunction with the composite, for example, byblending an element with the reactive composition prior to cure, byhaving the reactive composition coated and cured on the element, bymixing or blending the element with the cured composition, by coatingthe element onto the cured composition, by coating or adhering theelement onto the reactive composition which in turn is coated ontoanother element, by having the cured composition disposed within theelement, by having the cured composition distributed or dispersedthroughout the element, or any number of other useful formats. Thecomposite compositions of the invention are not particularly limited asto the additional elements combined therewith, nor by the particularformat employed in use thereof.

In embodiments, the composite composition is a cured composition coatedover at least part of the available surface of sand particles. Sand ofvarying grit size is a natural product that provides a useful amount ofsurface area for applications such as water remediation, does not softenor degrade during the curing process, and adheres strongly to the curedcompositions after coating and curing. The reactive compositions areapplied by conventional spray or immersion coating, followed in someembodiments by a simple curing process.

In one such embodiment, the composite composition is a cured compositioncoated over at least part of the available surface of sand particles,wherein the cured composition further has additional particles adheredthereto. In such embodiments, reactive compositions are coated onto thesand and then coated with one or more additional particulates such asclay, metal oxides, zeolites, or synthetic ion exchange materials. Thecomposite is heated sufficiently to form the cured composition. We havefound that using this technique, the cured composition adheres stronglyto the additional particulates as well as to the sand, forming a stablecomposite composition. In this manner, additional desirable propertiesare imparted to the composite compositions of the invention. Forexample, in embodiments where the additional particulate is clay, thenatural ion exchange capacity of the clay is imparted, providing theability of the composite composition to adsorb e.g. organic and ioniccompounds from water sources; further, the clay coating does not swellsufficiently to prevent water flow through media such as soil, makingsuch composite compositions ideal as water remediation compositions inmany applications. Additionally, the nature of the ionic environment, inconjunction with the tethered PAO chains present in the curedcomposition, together define a biphasic system that in turn affects thefate of an adsorbed species.

While clay coated sand is known in the art, it is used primarily forcosmetic reasons or to avoid certain problems associated with using pureclay in certain applications. These problems include dust, reduced waterpercolation, and the production of a slimy surface when wet. Forexample, U.S. Pat. Nos. 5,583,165 and 6,048,377 to Kviesitis teach theuse of a polymer, e.g. polyvinyl alcohols to glue clay to sand. Thefinal product is a clay coated and with a “clay color”. This productretains none of the clay's ion exchange capacity nor the water holdingcapacity and thus would be of little benefit to a soil profile via theclay's (or other particles) water holding or catalytic capability, orion exchange capacity.

In some embodiments, after sand particles are coated with the reactivecomposition, about 2-20% by weight, for example about 7-13% by weight,or about 10% by weight, of finely divided clay, colloidal oragglomerated silica, zeolites, nanoporous, mesoporous, or another porouscharcoal (carbon), oxides or hydroxides of calcium, aluminum, orsilicon, or a transition metal compound or catalyst including oxides,hydroxides, and organometallic derivatives of manganese, iron, titaniumaluminum, calcium, vanadium, chromium, tantalum, tungsten, palladium,platinum, silver, gold, copper, nickel, zinc, or a combination ormixture of two or more of these is slowly added to the sand withaccompanying agitation. In some embodiments, the incorporation offerromagnetic domains is accomplished by including particles of iron IIoxide, iron III oxide, nickel oxide, cobalt oxide, mixtures thereof,magnetic rare earth mixtures, and the like. The finely divided materialscan be microparticles or nanoparticles in addition to standard meshparticles. When all the finely divided material is sorbed onto the sand,the sand product is heated to about 100°-220° C., for example about 150°C. for about 10-120 minutes, for example about 45 minutes, to effectpolycondensation and crosslinking. The resulting composite compositionis pH adjusted with acid (e.g. hydrochloric, acetic, sulfuric, etc.) toa pH of about 4-8, for example about 6, and washed free of fines.Alternatively, the final polymerization can be acid catalyzed, therebyeliminating the need for a high cure temperature, but in someembodiments acid catalysis is deleterious to the one or more othermaterials employed to form the composite composition. Thus, the use ofeither higher temperatures or acid catalysis to effect condensation willbe selected by one of skill depending on the other elements of thecomposite composition that are present at the time of cure.

In some embodiments, particulates other than sand are advantageouslyemployed in a composite composition. Microparticles and nanoparticles ofclay, colloidal or agglomerated silica, zeolites, nanoporous,mesoporous, or another porous charcoal (carbon), oxides or hydroxides ofcalcium, aluminum, or silicon, or a transition metal compound orcatalyst including oxides, hydroxides, and organometallic derivatives ofmanganese, iron, titanium aluminum, calcium, vanadium, chromium,tantalum, tungsten, palladium, platinum, silver, gold, copper, nickel,zinc, or a combination or mixture of two or more of these, and the likeare employed in some embodiments as a substrate upon which the curedcompositions are disposed, for example by coating a reactive compositionon the substrate followed by curing. In other embodiments, theparticulates are admixed with the reactive compositions and thematerials are cured in contact with one another. The compositecompositions of the invention are not particularly limited as to thesize of the one or more particulates, or substrates, included within,disposed underneath, or disposed on the cured compositions.

C. Water Remediation Compositions and Applications Thereof

The cured compositions of the invention, and composite compositionsincluding the cured compositions, are useful in various forms andembodiments as water remediation compositions. In such applications, areactive composition selected for type and ratio of phenolic aldehydeprepolymer and ether adduct is applied to a surface by coating orspraying and subsequently cured to form a useful water remediationcomposition. Optionally one or more additional materials are added tothe reactive composition prior to curing.

In some embodiments, the surface to which the reactive composition isapplied is a part of the water remediation environment itself. In otherembodiments, the surface is a temporary carrier, such as a belt or drum,where the reactive composition is dried and cured; and the curedcomposition is collected after cure and applied to the water remediationenvironment, optionally after blending with one or more other suitablematerials. In still other embodiments, the surface to which the reactivecomposition is applied is a carrier surface intended to deliver thecured composition as a composite composition, along with other elementsoptionally included in the composite, to the remediation environment andsecure it therein.

Some water remediation embodiments are described herein below; it willbe appreciated that other such applications are easily envisioned andlie within the scope of the invention.

1. Soil Remediation and Soil Remediation Environments

In embodiments, a remediation environment wherein the cured compositionsof the invention are employed as water remediation compositions is asoil environment. Soil environments include lawns, golf greens,agricultural fields (i.e., gardens, vineyards, pastures, crop fields,fruit or vegetable orchards), nursery potting soil, or any other soilcontaining location that pesticides or other organic compounds areapplied or into which undesirable or excess compounds are leached (i.e.,industrial facilities, waste storage or treatment facilities, job sites,construction sites, chemical factories, weapon facilities, etc.). Inmany embodiments, movement of compounds through soils is facilitated bythe movement of water. Amounts of even the most hydrophobic compoundsare carried along with water within the soil and delivered to plants,insects, animals, and fresh water sources such as streams, rivers,sedimentation ponds, and lakes. The compounds are then taken up by theseentities, wherein even beneficial compounds such as fertilizers causeunintended consequences when present in excess. Excess fertilizer forlawns and crop fields, for example, are known to cause blooms of algaein fresh water when excess amounts are transferred via water in thesoil; such blooms, in turn, deplete the freshwater sources of oxygen.Thus, the water remediation compositions of the invention areadvantageously placed in soils where undesirable compounds, or harmfulamounts of otherwise harmless or beneficial compounds are located. Thewater remediation compositions of the invention are capable, in variousembodiments, of adsorbing excess fertilizers, pesticides, herbicides, ornematicides that otherwise can leach into groundwater and fresh watersources. Additionally, the water remediation compositions of theinvention are capable, in various embodiments, of adsorbing undesirablechemicals inadvertently introduced into soils. Such undesirablechemicals include those leaching into the soil from landfills,construction sites, waste containment sites, and the like.

In embodiments, because the cured compositions of the present inventionare easily affixed or coated onto a number of substrates of differentsizes and material composition prior to use, composite compositions ofthe invention are usefully employed as water remediation compositionswithin the soil or similar growth media. When placed strategically insuch water remediation environments, the cured compositions adsorborganic compounds carried by water within the soil. Depending on thesubstrate onto which the cured compositions are coated and othermaterials added, the composite compositions also affect, in variousembodiments, properties of the soil or media such as ionic content,percolativity, consistency, ability to support plant growth,oxygenation, nutrient retention, moisture retention, or combinations oftwo or more such properties.

In some such embodiments, soil remediation is enabled by employing thefollowing method to form a composite composition that is applied tosoil:

-   -   a) coating a reactive composition onto sand particles;    -   b) mixing a quantity of an ion exchange material with the coated        sand particles;    -   c) heating the mixture to a temperature wherein polycondensation        of the reactive composition occurs, resulting in a cured        composition; and    -   d) adding the cured composition to the soil to be amended.        In embodiments, the composite composition includes clay        particles to impart ion exchange capacity, thereby enabling        retention of fertilization cations from the water present in the        soil. Also, the clay's inherent anion exchange capacity enables        the retention of phosphate and silicate. The resulting composite        composition reduces leaching of applied fertilizer, keeping        nutrients in the root zone and thus preventing environmental        contamination. In some embodiments, the composite composition        includes iron hydroxide to impart anion exchange capacity.

In embodiments the composite composition facilitates percolation ofwater by retaining the porosity of the sand. Simply adding pure clay tosoil would result in both swelling of the clay and percolation of fineclay particles through the soil, where they tend to agglomerate orotherwise accumulate and subsequently clog pores and channels present inthe soil, thereby impeding percolation. In embodiments the compositecompositions adhere the clay to the coated sand, preventing clogging ofpores and channels, while maintaining the presence of clay in the soil.The presence of the clay attached to the composite compositions enhancesthe water holding capacity of the soil, which in turn leads to reducedstress of plants grown in the soil when drought conditions arise.

Additionally, we have found that the composite composition is resistantto the formation of hydrophobic surfaces known to arise in uncoatedsand, for example when water having a high content of mineral such ascalcium salts are contacted therewith. Sand coated with solely the curedcomposition provides this effect; the effect is not diminished by thepresence of clay. Fully wetting out the composite compositions of theinvention is advantageous because such intimate contact allows theadsorbing, ion-exchange, and water retention properties of the compositecompositions to be fully realized. Additionally, hydrophobicparticulates result in irrigation water channeling around affectedareas. Turf, trees, crops, and the like within these areas canexperience severe water stress.

Methods of introducing the soil remediation compositions of theinvention to the soil in effective soil and water remediationenvironments include top dressing periodically with cured compositionsand composite compositions of the present invention as well asbackfilling holes which result from conventional aeration activitiescarried out e.g. in turf or crop field areas. Another method ofintroducing the water remediation compositions of the invention to thesoil in effective soil and water remediation environments utilizes anunderground pipe system that collects water at a centralized location.This may be one or more sloping trenches lined with soil-filter fabricand filled with gravel (French drains), or a perforated pipe with theperforations facing the bottom of the trench and connected to a soliddrain line provides more efficient draining, or other subterraneandrainage systems. In one such embodiment, the water remediationcompositions are added to the soil-filter fabric, in another embodimentthe water remediation compositions are added to the gravel. In yetanother embodiment, the water remediation compositions are one componentof a filter through which water or effluent flows, located for exampleat a centralized location. In some such embodiments, the filter isconstructed so that it is easily replaced.

In various embodiments, an underground pipe and/or filter system is usedin conjunction with golf courses, sports fields, lawns, agriculturalfields, or in any location that pesticides or other organic compoundsare applied such as industrial facilities, waste storage and treatmentfacilities, job sites, construction sites, chemical factories, weaponsfacilities, and the like.

a. Herbicides

The cured compositions and composite compositions of the invention areuseful to bind and prevent the dispersal or leaching of herbicidalcompounds from the soil into unintended areas such as freshwatersources, aquifers, and the like. Her-bicidal compounds are primarilyused for weed control and many are well known. Herbicides are basicallygrouped according to their chemical structures, which include but arenot limited to triazines such as indazaflam, sold by Bayer AG ofLeverkusen, Germany under the trade name SPECTICLE®, as well asphenylureas, carbamates, phenoxyalkanoic acids, aryloxyphenoxypropanoicacids, (phenoxyacids), sulphonylureus, uracils, pyridazines, amides,dinitroanilines, benzonitriles, triazinone, cyclohexanediones, andothers (see, e.g. Tekel and Kovacicova, 1993; Tadeo et al., 1996;Gronwald, 1994). Herbicidal compounds commonly used on USGA golf greensprovide a representative sampling of herbicides that are commonlyemployed in non-crop lawns and fields. A listing of such herbicides andtheir properties can be found listed at the internet addresshttp://www.usga.org/green.

b. Insecticides

The cured compositions and composite compositions of the invention areuseful to bind and prevent the dispersal or leaching of insecticidalcompounds from the soil into unintended areas such as freshwatersources, aquifers, and the like. Insecticides are used to control insectpopulations; some work by killing insects and others work to preventreproduction thereof. Examples of insecticides that are suitablyadsorbed by the cured compositions and composite compositions of theinvention include Aldicarb, Allethrin, Ambush, Aminocarb, APM, Basudin,Bloallethrin, Bioremethrin, Biphenthrin, Bufencarb, Butacarb, butoxide,Carbanolate, Carbaryl, Carbofuran, Cinerin 1, Cinerin 11, Counter,Cyfluthrin, Cygon, Cyhalothrin, Cymbush, Cypermethrin, Cythion, Dasanit,Decis, Deltamethrin, Diazinon, Dibrom, Dimethoate 480, Dioxacarb, Dipet,Dyfonate, Dylox, Endosulfan, Ethidimuron, Fenpropathrin, Fenvalerate,Flucyrintae, Fluvalinate, Furadan, Guthion, Hopper Stopper, Imidan,Jasmolin 1, Jasmolin 11, Lagon, Lannate, Lorsban, Malathion,Metasystox-R, Methomyl, Methoxychlor, Mexacarbate, Monitor, Ortho,Oxamyl, Parathion, Permethrin, Piperonyl, Pirimor, Pounce, Promecarb,Pyrethrin 1, Pyrethrin 11, Pyrinex, Resmethrin, Ripcord, Sevimol, Sevin,Sniper, Supracide, Tetramethrin, Thimet, Thiodan, and Tralomethrin; alsosee, e.g. Chen and Wang, 1996; Yang et al., 1996, andhttp://www.gov.sk.ca/ajfood/cpg/iccont.htm). Insecticidal compoundscommonly used on USGA golf greens and their properties are listed at theinternet address http:/www.usga.org/green/table3.html.

c. Fungicides

The cured compositions and composite compositions of the invention areuseful to bind and prevent the dispersal or leaching of fungicidalcompounds from the soil into unintended areas such as freshwatersources, aquifers, and the like. Fungicides adsorbed by the curedcompositions and composite compositions of the invention include theclass Strobilurins, including e.g. azoxystrobin, sold by SyngentaInternational AG of Basel, Switzerland under the trade name HERITAGE®;pyraclostrobin, sold by BASF® SE of Ludwigshafen am Rhein, Germany underthe trade name INSIGNIA®; and trifloxystrobin, sold by Bayer AG ofLeverkusen, Germany as a mixture with triadimefon under the trade nameTARTAN®. Other fungicides adsorbed by the cured compositions andcomposite compositions of the invention include Benomyl, Captan,Chlorothalonil, Copper Sulfate, Cyproconazole, Dodine, Flusilazole,Flutolanil (sold by Bayer under the trade name PROSTAR®), Fosetyl-Al,Gallex, Mancozeb, Metalaxyl, Prochloraz, Propiconazole, Tebuconazole,Thiophanate Methyl, Triadimenol, Tridimefon, Triphenyltin hydroxide andZiram; also see, e.g. Shishkoff,http://www.bonsaiweb.com/forum/articles/arts/fungicide.html;http://cygnus.tamu.edu/Texiab/Nuts/Pecan/pecanf.html; and Hollomon,1993. Additional, fungicidal compounds, including trade and commonnames, may be found in Table 2 at the websitehttp://www.missouriedu/-extbsc/turflfundesc.htm. Areas such asagricultural, turf, and sport fields (golf course, tennis lawns, etc.)frequently are treated with substantial amounts of organic fungicides.Fungicidal compounds commonly used on USGA golf greens and theirproperties are listed at the internet addresshttp://www.usga.org/green/table3/html.

d. Nematicides

The cured compositions and composite compositions of the invention areuseful to bind and prevent the dispersal or leaching of nematicidalcompounds from the soil into unintended areas such as freshwatersources, aquifers, and the like. Nematicidal compounds are numerous.Nematicides adsorbed by the cured compositions and compositecompositions of the invention include those found athttp://www.acesag.auburn.edu/depart/ipm/Nematode.htm andhttp://www.missouri.edu/-extbsc/turfifundesc.htm. Some nematicidalcompounds that are commonly used on USGA golf greens and theirproperties are listed at the internet address http://www.usga.org/green.

Fenamiphos is one such nematicide. It is an anticholinesterase compound(Nemacurg, Bayer Crop Protection, Kansas City, Mo.) widely used fornematode control on soils, and in particular golf course greens andfairways. There are few labeled alternatives to this pesticide. Snyderand Cisar (1993) observed considerable leaching of fenamiphosmetabolites (sulfoxides and sulfones) following fenamiphos applicationto a USGA green. Leaching of the metabolites, and to a lesser extent theparent compound, greatly exceeded that of all other organophosphatesexamined (Snyder and Cisar, 2001 and 1995; Snyder, Elliott and Cisar,2001). Because fenamiphos has been observed in nearby waters in oradjacent to golf courses (Swancar, 1996), and because of ahighly-publicized fish kill (Zaneski, 1994), regulations have beenissued for limiting fenamiphos use on golf courses. The curedcompositions and composite compositions of the invention are ofparticular utility in conjunction with fenamiphos to prevent or greatlyreduce leaching of the compound and its metabolites.

e. Plant Hormones

The cured compositions and composite compositions of the invention areuseful to bind and prevent the dispersal or leaching of plant hormones,such as plant growth regulating materials, from the soil into unintendedareas such as freshwater sources, aquifers, and the like. Plant hormonesadsorbed by the cured compositions and composite compositions of theinvention include brassinolides, indoleacetic acid, indolebutyric acid,gibberilins, and cytokinins.

f. Additional Agrochemicals

The cured compositions and composite compositions of the invention arealso useful to bind and prevent the dispersal or leaching of one or acombination of two or more of the agrochemicals selected from thefollowing nonlimiting list: 3336 PLUS™ (thiophanate-methyl) (obtainedfrom the Cleary Chemical Corporation of Dayton, N.J.); FORE RAINSHIELD™(mancozeb) (obtained from the Dow Chemical Company of Midland, Mich.);BANOL™ (propyl-3(3-dimethylamino) propyl)carbamate hydrochloride(obtained from Bayer AG of Leverkusen, Germany); CHIPCO™ SIGNATURE™fosetyl aluminum (obtained from Bayer AG); and various agrochemicalproducts sold by Syngenta International AG of Basel, Switzerland underthe following trade names: herbicides such as BARRICADE™ 4FL, BARRICADE™65WG, DEPARTURE™, FUSILADE™ II Turf and Ornamental, MONUMENT™75WG,PENNANT™ MAGNUM, PRINCEP™ LIQUID, REFUGE™, REWARD™ Landscape andAquatic, and TENACITY™; fungicides such as BANNER™ MAXX, BANNER™ MAXXII, CONCERT™ II, DACONIL™ ACTION, DACONIL™ ULTREX TURF CARE®, DACONIL™WEATHER STIK™, DACONIL™ ZN FLOWABLE, HEADWAY™, HEADWAY™ G, HERITAGE™,HERITAGE™ G, HERITAGE™ TL, HURRICANE™, INSTRATAT™, MEDALLION™, MICORA™,PALLADIUM™, RENOWN™, and SUBDUE™ MAXX; insecticides such as AVID™ 0.15EC, AWARD™, CITATION™, ENDEAVOR™, FLAGSHIP™ 0.22G, FLAGSHIP™ 25WG,MERIDIAN™ 0.33G, MERIDIAN™ 25WG, SCIMITAR™ CS, and SCIMITAR™ GC; andplant growth regulators such as BONZI™, PRIMO™ MAXX, and TRIMMIT™ 2SC.It will be appreciated that this list is not exclusive and other suchcompounds and in particular agrochemicals not listed herein are alsousefully employed in conjunction with the cured compositions of theinvention.

2. Wastewater and Related Remediation

In embodiments, a remediation environment wherein the cured compositionsor composite compositions of the invention are employed as waterremediation compositions is an aqueous solution or dispersion. Inembodiments, the cured compositions or composite compositions of theinvention are employed as part of a treatment process or facility foraqueous solutions containing or suspected to contain organic compoundsand/or ionic moieties e.g., sewage, groundwater, wastewater, leachate,or industrial runoff. In some embodiments, water collected at a commonfacility is contacted with a cured composition of the present inventionto reduce the levels of organic compounds, such as pesticides in thewater. Water treatment systems are well known to those of skill in theart and include, but are not limited to, Sequencing Batch BiologicalReactor (SBA), continuous activated sludge, trickling filter, aeratedlagoon, and anaerobic filter. Such systems, and others, are adapted totreat organic compounds by employing the cured compositions of thisinvention. Additionally, as is described above, certain compositecompositions have further properties, such as ion exchange properties,that are usefully employed in conjunction with water remediation. Suchcomposite compositions are similarly useful in aqueous solutionremediation environments.

In some embodiments, the aqueous solution is treated by contacting thewater with particles including the water remediation composition in abatch method. In embodiments, such batch methods include:

-   -   a) adding particles including or consisting essentially of a        cured composition to an aqueous solution containing, or        suspected to contain, one or more organic compounds or        microorganisms;    -   b) agitating the particles in the aqueous solution for a        sufficient period of time to provide for adsorption of at least        a portion of the organic compounds, and    -   c) separating the particles from the purified aqueous solution.        In some embodiments of the method, the particles are composite        particles. In some such embodiments, the composite particles        further include clay, and the agitation further provides for ion        exchange of ionic moieties present in the aqueous solution. In        some embodiments the composite particles include aluminum        hydroxide, wherein the resulting zeta potential of the composite        particles will remove e.g. viruses. In some embodiments of the        method, separation is accomplished by sedimentation,        centrifugation, or filtration through a size selective porous        membrane, fritted glass filter, paper filter, and the like.

In some embodiments, the aqueous solution is treated by contacting thewater with particles including the water remediation composition byflowing through a column including a water remediation composition or by

-   -   a) coating fibers of a nonwoven filter media with the reactive        composition;    -   b) curing the reactive composition to provide a fibrous        composite composition;    -   c) placing one or more layers of the fibrous composite        composition in a flow pathway for the aqueous solution, and    -   d) flowing the aqueous solution through the flow pathway to        provide for adsorption of at least a portion of the organic        compounds.        In some embodiments of the method, particles or composite        particles containing the cured compositions are dispersed within        the nonwoven fibers, or sandwiched between filter media layers        instead of, or in addition to, coating fiber with the        compositions of the invention. In some embodiments, prior to        curing the reactive composition, one or more elements are added        to the reactive composition; in some such embodiments, the        element added is particulate clay. In such embodiments, the        aqueous solution contains or is suspected to contain one or more        ionic moieties, and flowing the aqueous solution includes        adsorption of at least a portion of ionic moieties present in        the aqueous solution.

An alternative embodiment includes coating a film or a glass plate witha reactive composition and curing it, optionally including one or moreadditional elements, and submersing the composite film composition inthe aqueous solution.

U.S. Pat. No. 4,511,657 teaches a method of treating chemical wastesusing an SBA system comprising activated sludges. In embodiments, themethod of the '657 patent employ the cured compositions of theinvention, wherein the cured compositions or composite compositions areadded to the biological organism containing activated sludge, orutilized in one or more separate tanks comprising activated sludge, orused in lieu of the biological material. The latter obviates the need tomaintain the viability of living organisms.

U.S. Pat. No. 5,685,981 teaches a filter system. In various embodiments,filter apparatuses have an intake port, a chamber, and an outlet port.Conventionally, activated carbon is disposed within a filter chamber toadsorb organic compounds. Activated carbons are available in differentgrades and with different binding activities. However, not all gradesperform well in all purposes and effective grades tend to be expensive.Cured compositions and composite compositions of the invention are used,in various embodiments, in the place of or in addition to activatedcarbon in the chamber of a filter system. In embodiments, the presenceof the cured compositions and composite compositions of the inventionincrease the range of organic compounds adsorbed from an aqueoussolution.

U.S. Pat. No. 4,995,969 teaches a biological living-filter system forthe treatment of sanitary landfill leachate which includes a treatmentbasin lined with a water impervious material and filled with anorganically enriched treatment medium conducive to maintaining apopulation of micro-organisms. The system also includes leachatetolerant plants growing in the treatment medium. This system, modifiedto include one or more cured compositions or composite compositions ofthe invention, increases the range of compounds adsorbed.

Alternatively, one or more cured compositions and composite compositionsof the invention are useful in conjunction with in a landfill leachatetreatment system similar to that taught by U.S. Pat. No. 4,995,969, inaddition to or in lieu of the biological material described therein. Useof one or more cured compositions and composite compositions of theinvention in such a manner obviates the need to establish and maintain aliving ecosystem.

In a related embodiment, treatment of water phases containing heavymetals or ions thereof is carried out employing the cured compositionsand composite compositions of the invention. The partitioning behaviorof the PAO component of the cured compositions and compositecompositions of the invention is affected in the presence of bases suchas NaOH or (NH₄)₂SO₄, wherein their presence in the water phase results,in embodiments, in the uptake of heavy metal ions from the aqueoussolution. Such uptake is advantageously employed by the curedcompositions of the invention, wherein PAO is tethered within the curednetwork polymer, effectively sequestering such metal atoms and ionswithin a phase that is easily separated from the water phase. Thispartitioning behavior is known with respect to PAOs such as polyethyleneoxide, as reported e.g. by Rogers et al., Sep. Sci. and Tech., 30(7-9),1203-1217, 1995. Water phases treatable using the cured compositions andcomposite compositions of the invention include water entrained in e.g.soil and the like where the water has entrained within it heavy metalsor ions thereof. Examples of heavy metal ions usefully sequestered bythe cured compositions and composite compositions of the inventioninclude cesium and strontium ions, oxyanions such as technetate,chromate, molybdate, tungstate, and orthovanadate.

Additional lyotropic anions useful in providing an aqueous PAOliquid/liquid biphase form salts with ammonium or alkali metal cationsinclude hydroxide, fluoride, carbonate, silicate, sulfate, phosphate,dihydrogen phosphate, hydrogen phosphate, formate, succinate, acetate,tartrate, citrate, thiocyanate, thiosulfate, fluorosilicate,orthosilicate, hydroxyethane-1,1-diphosphonate (-2, -3, and -4 anionforms), and vinylidene-1,1-diphosphonate (-2, -3, and -4 anion forms).Without being limited by theory, we believe that the presence of clayprovides a colloidal electrolyte that causes biphase formation at thesurface of a composite particle.

3. Medical Remediation

In embodiments, the cured compositions and composite compositions of theinvention are useful in one or more medical remediation environmentswherein the waterbased solutions/dispersions are bodily fluids.Applications such as purification of toxins or other impurities fromblood, kidney dialysis, and the like are addressed by employing thecured compositions and composite compositions of the invention. Indialysis and blood purification, for example, filter cartridges that insome embodiments are the same or similar to those described above forwater remediation applications are similarly useful herein. Typically,different types of e.g. filter media, cartridge materials, and the likeare employed for medical applications. Further, the compositecompositions of the invention employ, in embodiments, elements capableof withstanding sterilization; conventional sterilization employs heatand/or steam and pressure, such as in an autoclave; or chemicaltreatment such as treatments with ethylene oxide, chlorine dioxide,hydrogen peroxide, and the like; or radiation treatments with gamma raysor electron beams.

When used in place of or in addition to conventional medicalpurification or dialysis materials, the cured compositions and compositecompositions of the invention increase or augment the range of compoundsadvantageously scavenged from bodily fluids. Organic compounds arescavenged by the cured compositions, while composite compositionsinclude, in embodiments, ion exchanging materials or other materialsdesigned to scavenge specific compounds or classes of compounds.Additionally, the cured compositions of the invention facilitaterecovery of pertechnate from radiodye waste streams.

4. Personal Care Remediation

In embodiments, the cured compositions and composite compositions of theinvention are useful in one or more personal care remediationenvironments wherein the waterbased solutions/dispersions are excretedbodily fluids. Excreted bodily fluids include urine, pus, blood, menses,mucosal substances, drainage from wounds or surgical incisions, and thelike. Such bodily fluids often contain agents that cause odors to arise.Remediation of such fluids is accomplished by scavenging the organiccompounds causing odors, or the agents giving rise to the odors, or bothfrom the excreted bodily fluids. Such agents and compounds are addressedby employing the cured compositions and composite compositions of theinvention.

Articles conventionally employed to absorb excreted bodily fluidsinclude bandages, diapers, feminine hygiene products, and the like;collectively, these articles are referred to as personal hygieneproducts. In embodiments, one or more personal hygiene products ismodified to include one or more cured compositions and compositecompositions of the invention. Many such personal hygiene productsemploy nonwoven fabrics therein. In some such embodiments, fibers of anonwoven fabric are coated with the reactive composition, then cured toform a composite composition that is incorporated into a diaper,bandage, and the like. In other such embodiments, one or moreparticulates are formed from, or with, the cured compositions of theinvention and the particulates are entrapped in a nonwoven fabric forthe purpose of remediation.

When used in place of or in addition to conventional materials andarticles employed for absorption of excreted bodily fluids, the curedcompositions and composite compositions of the invention increase oraugment the range of compounds advantageously scavenged. Organiccompounds are scavenged by the cured compositions, while compositecompositions include, in embodiments, ion exchanging materials or othermaterials designed to scavenge specific compounds or classes ofcompounds.

D. Controlled Release Compositions and Applications Thereof

In embodiments, the cured compositions and composite compositions of theinvention are suitably employed as controlled release compositions.Controlled release compositions are compositions that are pre-loadedwith a compound or a mixture of compounds such that, when the loadedcontrolled release composition is placed in a release environment, itreleases the compound or mixture of compounds at a predictable rate thatis slower than the simple addition of the same amount of that compoundor mixture thereof into the release environment. In embodiments, thecontrolled release provides a period during which there is a steadystate concentration of the compound or mixture thereof in the releaseenvironment; in other embodiments, the range of concentration in therelease environment varies continuously over time.

In embodiments, a controlled release composition is characterized inthat the concentration of the compound or mixture thereof delivered bythe release composition into the release environment is, at any givenpoint in time, less than the initial concentration observed in therelease environment when the compound or mixture thereof is added toenvironment in the absence of the controlled release composition. Inother embodiments, a controlled release composition is characterized inthat the presence of the compound or mixture thereof, delivered by therelease composition into the release environment, is detectable for aperiod of time after the depletion of the compound or mixture thereofafter addition to the release environment in the absence of thecontrolled release composition.

Pre-loading of a cured composition of the invention for use as acontrolled release composition is accomplished using any of severalavailable methods. For example, immersion of the cured composition orcomposite composition into a concentrated solution of the compound to bereleased is one suitable method for pre-loading the controlled releasecomposition. In some embodiments, rather than a solution of thecompound, the neat compound in liquid form is used. In some embodiments,the addition of heat and/or pressure is advantageously employed toaccomplish the pre-loading. In other embodiments, the compound to bereleased is sprayed, in solution or in neat form, onto the curedcomposition or composite composition wherein the compound is adsorbed;in some such embodiments, heat and/or pressure is also suitablyemployed. In still other embodiments, the compound is added to thereactive composition and is thus entrained within the crosslinked matrixat the time of curing to form the cured composition or compositecomposition. In still other embodiments, the compound is applied to anelement for forming a composite composition, and the element is added tothe reactive composition such that curing results in a compositecomposition. In still other embodiments, the compound is added inconjunction with a surfactant, wherein the surfactant associatesnon-covalently with the cured or reactive composition, and the compoundis associated non-covalently with the surfactant. Examples of suitableelements for delivering the compound to the reactive composition includeclay, activated carbon, porous silica, or some other particle; or apolymer, crown ether, cyclodextrin, or other compound that forms aclathrate or clathrate-like composition with the compound to bereleased.

The controlled release compositions of the invention are useful asadjuvants or delivery vehicles for the controlled release of organiccompounds into environments containing liquid water.

1. Controlled Release of Soil Treatment Agents

The controlled release compositions of the invention are useful asadjuvants or delivery vehicles for the controlled release of soiltreatment agents into water containing soil environments. Suitable soiltreatment agents including herbicides, organic pesticides (includingnematicides, insecticides, fungicides, and microbicides). Such materialsare pre-loaded into a cured composition or composite composition of theinvention for controlled release upon contacting a lawn, golf green,agricultural field (i.e., garden, vineyard, pasture, crop field, fruitor vegetable orchard), nursery potting soil, and the like.

The ability to coat and cure the reactive compositions of the inventiononto inert and/or ecologically harmless substrates, such as sandparticles, provides a biocompatible matrix for not only the controlledrelease of fertilizers or pesticides to a target area withoutintroducing incompatible or unsuitable adjuvants or substrates into theenvironment, but also provides an easily used form to accomplish thecontrolled release composition to the release environment. Further, theability to adhere e.g. clay or another ion exchange composition to suchcoated sand particles provides the means to enhance cation and anionexchange, and moisture and nutrient retention capacities of the soilwithout concurrent reduction in percolation rate.

In embodiments, the controlled release compositions of the invention arealso useful in this role when employed as soil remediation compositions.That is, instead of pre-loading the controlled release compositions ofthe invention before addition thereof to a soil environment, suchcompositions are useful to adsorb and retain excess fertilizers orpesticides when such are applied as-is to a soil environment; thecompositions then slowly release these compounds back to the soil. Insuch embodiments, the cured compositions or composite compositions ofthe invention prevent leachates from reaching fresh water sources and atthe same time provide for the prolonged release of low levels of thecompounds into the soil.

The controlled release compositions of the invention are useful toprovide for controlled release in soil, when preloaded with one or acombination of two or more of the following agrochemicals selected fromthe following nonlimiting list of compounds: 3336 PLUS™(thiophanate-methyl) (obtained from the Cleary Chemical Corporation ofDayton, N.J.); FORE RAINSHIELD™ (mancozeb) (obtained from the DowChemical Company of Midland, Mich.); BANOL™ (propyl-3(3-dimethylamino)propyl)carbamate hydrochloride (obtained from Bayer AG of Leverkusen,Germany); CHIPCO™ SIGNATURE™ fosetyl aluminum (obtained from Bayer AG);and various agrochemical products sold by Syngenta International AG ofBasel, Switzerland under the following trade names: herbicides such asBARRICADE™ 4FL, BARRICADE™ 65WG, DEPARTURE™, FUSILADE™ II Turf andOrnamental, MONUMENT™ 75WG, PENNANT™ MAGNUM, PRINCEP™ LIQUID, REFUGE™,REWARD™ Landscape and Aquatic, and TENACITY™; fungicides such as BANNER™MAXX, BANNER™ MAXX II, CONCERT™ II, DACONIL™ ACTION, DACONIL™ ULTREXTURF CARE®, DACONIL™ WEATHER STIK™, DACONIL™ ZN FLOWABLE, HEADWAY™,HEADWAY™ G, HERITAGE™, HERITAGE™ G, HERITAGE™ TL, HURRICANE™,INSTRATAT™, MEDALLION™, MICORA™, PALLADIUM™, RENOWN™, and SUBDUE™ MAXX;insecticides such as AVID™ 0.15 EC, AWARD™, CITATION™, ENDEAVOR™,FLAGSHIP™ 0.22G, FLAGSHIP™ 25WG, MERIDIAN™ 0.33G, MERIDIAN™ 25WG,SCIMITAR™ CS, and SCIMITAR™ GC; and plant growth regulators such asBONZI™, PRIMO™ MAXX, and TRIMMIT™ 2SC. It will be appreciated that thislist is not exclusive and other such compounds and in particularagrochemicals not listed herein are also usefully employed inconjunction with the cured compositions of the invention.

2. Controlled Release of Insecticides and Insect Attractants.

The controlled release compositions of the invention are useful asadjuvants or delivery vehicles for the controlled release of one or moreinsecticides. As used herein, the term “insecticide” means a compound ormixture of compounds that kills insects, repels insects, or providessome other effect that mitigates harmful effects of insects or otherwisereduces their numbers; or a combination of one or more such effects.Insect attractants include compounds and mixtures thereof to attractinsects. In various embodiments, the purpose of attracting insects is tobring them to a specific location or to attract them away from anotherlocation. One example of an insect attractant is a pheromone.

One example of an insecticide is a termiticide. Termiticide solutions oremulsions are conventionally applied to soak into the voids in the soilto create a “barrier” that repels termites from e.g. wooden buildingstructures or construction areas prior to pouring of a foundation slabfor a new building. Examples of commonly used termiticides includeFipronil, sold by BASF® SE of Ludwigshafen am Rhein, Germany under thename TERMIDOR®, and Imidocloprid, sold by Bayer AG of Leverkusen,Germany under the trade name PREMISE®. Termiticides are conventionallyapplied in emulsion form with the purpose of adhering the emulsion toorganic carbon sources. In such uses, sandy soils provide more completepercolation, but poor bonding (and thus, lower overall efficacy becausethe termiticide leaches or washes through the soil); and clay-rich soilsoffer better bonding in some embodiments but provide fewer gaps for theemulsion to penetrate. If the soil is saturated with water, or if it istoo cold, is it not practicable to apply the chemical at the requiredlabel rate. In embodiments, the controlled release compositions of theinvention are employed to provide a means to apply the termiticide ineffective amounts to targeted areas that are otherwise not practicable,or to increase the longevity of termiticide treatment of the soil. Itwill be understood by those of skill that the compositions of theinvention are employed, in various embodiments, as applied to the soilprior to application of the termiticide, or as pre-loaded with thetermiticide. The pre-loaded composition is more preferred wherepercolation of the termiticide emulsion or solution is hampered.

3. Controlled Release of Pharmaceuticals

The controlled release compositions of the invention are useful asadjuvants or delivery vehicles for the controlled release ofpharmaceutical compounds, that is, drugs or other medicaments, directlyinto biological systems. For example, adhesive patches areconventionally employed for controlled release of pharmaceuticalcompounds into a human patient, where such drugs are able to cross theskin barrier (transdermal) or a mucosal barrier (transmucosal) and beabsorbed into the bloodstream. In some cases, animals such as livestockare similarly benefitted by the use of such controlled release articles.Transdermal or transmucosal patches containing controlled releasecompositions of the invention pre-loaded with one or more pharmaceuticalcompounds are useful for providing controlled release and have theadvantages of being easy and inexpensive to manufacture and chemicallyinert to the body.

Many suitable embodiments of the cured compositions or compositecompositions of the invention are envisioned for such uses. For example,in a representative embodiment, a reactive composition is coated onto asection of polyester film, such as a 1″×1″ or 2″×2″ section, and one ormore medicaments added thereto. The reactive composition is cured toyield a composite composition. Then an adhesive is coated eithersubstantially around the edges of the composition, or over the entiretyof the composition, and the coated film employed as a transdermal patch.Similarly, nonwoven media or inert particles are coated with thereactive compositions containing one or more pharmaceuticals; similarly,particles are formed that include the cured composition and one or morepharmaceuticals. In other embodiments, the reactive compositions arecoated with particulates containing the pharmaceuticals.

Suitable pharmaceuticals employed in conjunction with the controlledrelease compositions of the invention include nicotine, painkillers,drugs for the treatment of skin conditions such as acne, psoriasis,eczema, and the like, antibiotics, antifungal, or antiviral drugs,insulin-control drugs, weight loss drugs, drugs for the regulation ofmental health conditions such as anti-depressants, anti-psychotics, andthe like, heart medications for arrhythmia, high blood pressure, and thelike, chemotherapy drugs, natural or synthetic steroids or hormones,dietary supplements and “neutraceutical” compounds and mixtures, orother compounds of therapeutic value for the human body and mixtures oftwo or more thereof.

Using techniques such as those described above, one or morepharmaceuticals are pre-loaded into a cured composition or compositecomposition of the invention for controlled release upon contact withhuman or animal skin or mucosal surfaces. The release is via diffusiveor microporous flow or a combination thereof depending on the nature ofthe cured composition and the composite composition in which the curedcomposition resides.

E. Additional Applications of the Compositions

In some embodiments, the cured compositions of the invention areusefully disposed as coatings on one or more medical device surfaces. Inimplantable devices, for example, it is known that polyethylene oxide(PEO) and polypropylene oxide (PPO) surfaces are “invisible” to thehuman body's various biological reaction systems triggered by e.g.protein or cell adhesion or pickup. The cured compositions of theinvention can be designed to have a majority weight percent compositionof PEO, for example between 50 wt % and 95 wt % PEO, while stillretaining a robust level of crosslinking that imparts durability to acoated surface. Adhesion of the cured compositions to metals, ceramics,thermoplastics, or thermosets commonly employed in medical devices isachieved by curing the reactive composition in situ or, in someembodiments, achieved by post-cure functionalization of e.g. gel-likecured compositions as described above. Thus, cured compositions of theinvention are formed in situ, in some embodiments, directly on thesurface of a medical device such as an artificial bone or bone sectionor joint, a stent, a valve, and the like to impart durable anti-foulingproperties thereto.

In some embodiments, the cured compositions or composite compositions ofthe invention are useful in scavenging one or more organic componentsfrom a gas, such as air, nitrogen, helium, oxygen, and the like.Volatile organic compounds, or VOCs, are often entrained in sources suchas industrial exhaust, incinerator facilities, and the like wherein itis desirable to scavenge VOCs in order to improve the quality of airdischarged. Industrial manufacturing of purified gases also requiresmeans to scavenge minor or trace amounts of VOCs therefrom. In some suchembodiments, the cured compositions or composite compositions of theinvention are useful to reduce or remove VOCs, thereby purifying thegas.

Other air purification applications addressed by incorporating the curedcompositions or composite compositions of the invention include passivesources of undesirable compounds in locations where air quality is anissue. For example, automobile cabin interiors, where off-gassing ofplasticizers or other impurities by plastic components is a recognizedproblem; similarly, interior living spaces where carpet or rug backingssimilarly are known to release harmful compounds are a known issue.

In various embodiments, the filtration type embodiments described aboveinclude the cured compositions or composite compositions and areemployed for the purposes of filtering a gaseous fluid instead of water.In passive sources of VOCs, coatings of the cured compositions on filmsor sachets included in an automobile interior, coated on particlesentrained in a carpet backing or provided as a layer beneath thebacking, and the like are useful embodiments employed to reduce orremove harmful or odorous VOCs from breathable air. The configuration,type of cured composition employed, and amount employed will be selectedby one of skill to address the particular gas purification application.

The foregoing is applicable to various compositions and articles of theinvention disclosure. The following examples and data further exemplifythe invention. The invention may be better understood with reference tothe following examples. These examples are intended to be representativeof specific embodiments of the invention, and are not intended aslimiting the scope of the invention.

F. Experimental Section

EXAMPLE 1

Synthesis of the bromide adduct of polyethylene glycol monomethyl etherwas carried out by adding 100 parts by weight of MPEG 5000 (polyethyleneglycol, 5000 avg. MW, monomethyl ether; obtained from Ineos Oxide ofSwitzerland) to a reaction vessel, followed by addition of 2 parts byweight of PBr₃ (obtained from GFS Chemical Co. Powell, Ohio) and heatingthe neat mixture for 3 hrs at 70° C. The product thus formed wascollected and used without further purification, and is referred to asMPEG-Br in subsequent sections below.

A reaction vessel was charged with 13.26 g BINDEX® 73 (obtained from theIndspec Chemical Corporation of Petrolia, Pa.) and 3.0 g of a 50 wt %solution of NaOH in water; the contents of the vessel were mixed. Then102 g of MPEG-Br was added in molten form, at about 70° C., slowly overa period of about 15 min. with stirring. The temperature of the mixturereached about 50° C. After an additional 1 hr of stirring, 250 g ofCASCOPHEN® M707 (obtained from MOMENTIVE™ Performance Materials, LLC ofColumbus, Ohio) was added and thoroughly mixed into the vessel to form aComposition A.

One kilogram of sand meeting the requirements set forth in “USGARecommendations for a Method of Putting Green Construction” (2004Revision), U.S. Golf Association Green Section Staff, publication PG1110 (publication available at http:/www.usga.org/Contentaspx?id-26124)and ASTM tests listed in Appendix I therein, and 10 g of Composition Awere combined in a Cleveland-type benchtop muller. The combination wasmixed for about 45 seconds. Then 8 g CASCOPHEN® W3154N (obtained fromMomentive™ Performance Materials), 3 g BAYERFERROX® 918LO (obtained fromLanxess AG of Leverkeusen, Germany (moving to Cologne, Germany in 2013))and 0.4 g phthalocyanine blue was added to the muller and thiscombination was mixed for about 45 seconds. Then 25 g Composition A wasadded to the muller and the combination was mixed for about 45 seconds.Then 70 g PANTHERCREEK® 200 bentonite (obtained from the AmericanColloid Company of Hoffman Estates, IL) was added to the muller and thecombination was mixed for about 1 minute to produce a coated sandproduct.

The coated sand was collected from the muller and heated to 135° C. forabout 30 minutes to yield a coated cured sand. The coated cured sand wascooled to room temperature and tested for cation exchange capacity aswell as soluble organic carbon.

EXAMPLE 2

In a reaction vessel, 4.6 g Bisphenol A (obtained from the AshlandChemical Co. of Ashland, Ky.) was mixed with 1.6 g 50% NaOH. Then 4.9 gof a 37% formaldehyde solution and 1 g of deionized water was added tothe vessel. The contents of the vessel were heated to 50° C. and stirredfor about 30 minutes to form Composition B.

In a separate vessel, 9.5 g BINDEX® 73 (obtained from the IndspecChemical Corporation of Petrolia, Pa.) was mixed with 4.8 g of a 50 wgt% NaOH solution in water. Composition B was added dropwise into thisover about 10 minutes with stirring. This mixture was allowed to reactfor 30 min with stirring. Then 102 g MPEG-Br was added in molten form,at about 70° C., slowly over a period of about 10 min with stirring andallowed to react with stirring for an additional approximately 30minutes. Then 250 g CASCOPHEN® M707 (obtained from MOMENTIVE™Performance Materials, LLC of Columbus, Ohio) was and thoroughly mixedto yield Composition C.

One kilogram of the same sand as used in Example 1 and 10 g CompositionC were combined in a Cleveland type benchtop muller. The combination wasmixed for about 45 seconds. Then 8 g CASCOPHEN® W3154N (obtained fromMomentive™ Performance Materials), 3 g BAYERFERROX® 918LO (obtained fromLanxess AG of Leverkeusen, Germany (moving to Cologne, Germany in 2013))and 0.4 g phthalocyanine blue was added to the muller and thiscombination was mixed for about 45 seconds. Then 28 g of Composition Cwas added to muller and the combination was mixed for about 45 seconds.Then 70 g PANTHERCREEK® 200 bentonite (obtained from the AmericanColloid Company of Hoffman Estates, IL) was added to the muller and thiscombination was mixed for about 1 minute to produce a coated sandproduct.

The coated sand was collected and heated to 135° C. for about 30 minutesto yield a coated cured sand. The coated cured sand was cooled to roomtemperature and tested for cation exchange capacity as well as solubleorganic carbon.

EXAMPLE 3

In a reaction vessel, 8.8 g resorcinol (obtained from Dynea USA, Inc. ofToledo, Ohio) was dissolved in 8 g of a 50 wgt % solution of NaOH inwater. Then 102 g MPEG-Br was added in molten form, at about 70° C.,slowly over a period of about 15 min with stirring. The resultingmixture was stirred for an additional approximately 30 minutes. Then 250g CASCOPHEN® OS M707 (obtained from MOMENTIVE™ Performance Materials,LLC of Columbus, Ohio) was added to the vessel with thorough mixing toyield Composition D.

One kilogram of the same sand as used in Example 1 and 10 g CompositionD were combined in a Cleveland-type benchtop muller. The combination wasmixed for about 45 seconds. Then 8 g CASCOPHEN® W3154N (obtained fromMOMENTIVE ™ Performance Materials), 3 g BAYERFERROX® 918LO (obtainedfrom Lanxess AG of Cologne, Germany) and 0.4 g phthalocyanine blue wereadded to the muller and the combination was mixed for about 45 seconds.Then 26 g of Composition D was added to the muller and the combinationwas mixed for about 45 seconds. Then 70 g PANTHERCREEK® 200 bentonite(obtained from the American Colloid Company of Hoffman Estates, IL) wasadded to the muller and the combination mixed for about 1 minute toproduce a coated sand product.

The coated sand was collected and heated to 135° C. for about 30 minutesto yield a coated cured sand. The coated cured sand was cooled to roomtemperature and tested for cation exchange capacity as well as solubleorganic carbon. Two drops of 0.5 wt % Methylene Blue dye in water wasadded to an aliquot of the coated sand in water and the slurry wasshaken briefly then allowed to stand for several minutes followed bydecanting the water from the sand; the sand was washed with clean water.The washed sand exhibited a purple sheen, characteristic of theassociation of the dye with the cation exchange sites of the clay.

EXAMPLE 4

In a reaction vessel, 100 g resorcinol (obtained from the IndspecChemical Corporation of Petrolia, Pa.) was dissolved in 100 g ofdeionized water. Then 2 g of oxalic acid was dissolved in the resorcinolsolution and the mixture was brought to reflux. Then 50 g of a solutionof 37% formaldehyde in water was added slowly to the refluxing mixturewith vigorous stirring. After the addition was completed the mixture wasallowed to stir under reflux conditions for about 1 hour to yieldComposition E.

Composition E is used, in conjunction with one or more brominatedalkylene oxide compounds and one or more phenolic aldehyde or resorcinolprepolymers, to form coated cured sand products using the generaltechniques outlined in Examples 1-3 above.

EXAMPLE 5

A 1 L Erlenmeyer flask was charged with 25.3 g deionized water and 12.65g BINDEX® 73 (obtained from the Indspec Chemical Corporation ofPetrolia, Pa.). The mixture in the flask was sparged with Argon gas.Then 6.4 g of a 50 w/w % solution of sodium hydroxide was added to theflask and the mixture and stirred until it appeared homogeneous. Then100 g MPEG 5000 Br was added slowly to the flask with vigorous mixing,over about 30 minutes; stirring was continued for an additional periodof about 45 minutes. Then 356 g of CASCOPHEN® OS 707M (obtained fromMOMENTIVE™ Performance Materials, LLC of Columbus, Ohio) was then addedto the flask with vigorous agitation.

About 25 g of this mixture was removed from the flask and added to 900 gsilica sand in a Cleveland-type laboratory benchtop muller and thecombination was thoroughly mixed. Then 8 g CASCOPHEN® W3154N-1 (obtainedfrom MOMENTIVE™ Performance Materials), 0.3 g phthalocyanine blue and 3g BAYERFERROX® 91LO Yellow (obtained from Lanxess AG of Cologne,Germany) were added to the muller and this combination was mixed forabout 1 minute. Then 70 g of PANTHER CREEK® 200 Calcium Bentonite(obtained from the American Colloid Company of Hoffman Estates, IL) wasadded to the muller and this combination was mixed for about 1 minute toresult in a coated sand product. The coated sand product was removedfrom the muller and placed in an oven set at 150° C.; once the materialreached 130° C., heating was continued for about 10 minutes. Then thecoated sand product was allowed to cool to ambient temperature. Aftercooling the pH of the coated sand was adjusted to about 5.5 by sprayingthe sand with 15% sulfuric acid solution.

Upon microscopic examination, the coated sand product was observed topossess a uniform coating including resin, pigment and clay. When asample of the coated sand was added to water and shaken, the coating wasinsoluble, but easily wettable; and no foaming was observed. Two dropsof 0.5 wt % Methylene Blue dye in water was added to the coated sand inwater and the slurry was shaken briefly then allowed to stand forseveral minutes followed by decanting the water from the sand; the sandwas rinsed with clean water. The sand exhibited a purple sheen,characteristic of the association of the dye with the cation exchangesites of the clay.

Sorption and desorption of ammonium ions to/from the coated sand productwas measured. A 1 g aliquot of the coated sand was added to a beakercontaining about 10 mL of a 0.1 wt % ammonium sulfate solution. The sandwas swirled periodically for about 30 minutes, then the liquid wasdecanted. The sand was washed with deionized water until no nitrogen wasdetected in the wash water. Then 10 mL of a 1 wt % calcium chloridesolution was added to the washed sand, mixed by agitation, and theliquid decanted and analyzed. The liquid contained 40 ppm nitrogen.Sorption and desorption of ammonium ions from the exchange sitesdemonstrates the continued activity of the clay within the composite.

EXAMPLE 6

A 500 ml mason jar was charged with 110 g resorcinol (obtained from theIndspec Chemical Corporation of Petrolia, Pa.) and 80 g deionized water,and the mixture was stirred and warmed until the resorcinol wasdissolved. Then 25 g of a 37 wt % formaldehyde solution in water wasadded with vigorous stirring, followed by slow addition of 1.8 g conc.H₂SO₄. The resulting mixture was stirred at ambient laboratorytemperature for about 8 hours. Then the pH was adjusted to 5.8 using16.5 g of a 50% w/w NaOH solution. The resultant resorcinol novalacproduct was found to be 57% solids.

Then 16 g of the resorcinol novalac product was removed from the jar andplaced in a fresh 500 ml mason jar equipped with a magnetic stir bar; 48g deionized H₂O was added to the jar and this mixture was stirred andsparged with Argon. Then 7.4 g 50% w/w NaOH solution was added to thejar with stirring. Then 100 g MPEG 5000 Br was added slowly to the jarover 30 minutes, accompanied by vigorous stirring. After the additionwas completed, stirring was continued for an additional 45 minutes. Then329 g CASCOPHEN® OS 707M (obtained from MOMENTIVE™ PerformanceMaterials, LLC of Columbus, Ohio) was added to the jar with vigorousstirring.

About 25 g of this mixture was removed from the flask and added to 900 gsilica sand in a Cleveland-type laboratory benchtop muller and thecombination was thoroughly mixed to coat the sand. Then 8 g CASCOPHEN®W3154N-1 (obtained from MOMENTIVE™ Performance Materials), 0.3 gphthalocyanine blue and 3 g BAYERFERROX® 91LO Yellow (obtained fromLanxess AG of Cologne, Germany) were added to the muller and thiscombination was mixed for about 1 minute. Then 70 g of PANTHER CREEK®200 Calcium Bentonite (obtained from the American Colloid Company ofHoffman Estates, IL) was added to the muller and this combination wasmixed for about 1 minute to result in a coated sand product. The coatedsand product was removed from the muller and heated in an oven set at150° C.; once the material reached 130° C., heating was continued forabout 10 minutes. Then the coated sand was allowed to cool to ambientlaboratory temperature. After cooling the pH of the coated sand wasadjusted to about 5.5 by spraying the sand with 15% sulfuric acidsolution.

Upon microscopic examination, the coated sand product was observed topossess a uniform coating including resin, pigment and clay. When asample of the coated sand was added to water and shaken, the coating wasinsoluble, but easily wettable; and no foaming was observed. Two dropsof 0.5 wt % Methylene Blue dye in water was added to the coated sand inwater and the slurry was shaken briefly then allowed to stand forseveral minutes followed by decanting the water from the sand; the sandwas rinsed with clean water. The sand exhibited a purple sheen,characteristic of the association of the dye with the cation exchangesites of the clay.

Sorption and desorption of ammonium ions was demonstrated using thetechniques and materials of Example 5. The results were similar to theresults described in Example 5.

Sorption and desorption of selected pesticides to/from the coated sandproduct was measured. Ten mg each of Chlorothalonil, Azoxstrobin,Paclobutrazol, and Propiconazole (all obtained from SyngentaInternational AG of Basel, Switzerland) were added to a single vialcontaining 4 ml acetone. Ten mg of a degradation product of severaltriazole fungicides, 1,2,4-triazole, was dissolved in 4 ml deionizedwater. Then 20 μL, of each of the two pesticide solutions (the watersolution of 1,2,4-triazole, and the acetone solution of theChlorothalonil, Azoxstrobin, Paclobutrazol, and Propiconazole) wereadded to each of six 200 ml glass vials, wherein each vial contained 10ml of water; the vial contents were agitated to mix the contents. Fourof these vials were charged with 40 g of water washed, dry coated sandproduct; two of these vials were charged with 40 g of the silica sandfrom which the coated sand products of this Example were made. The sixvials were then allowed to stand for two hours with agitation every 30minutes. Additional 15 ml aliquots of water were then added to each ofthe vials with agitation, then 4 ml of the liquid from each vial wasdecanted into a scintillation vial. Azoxstrobin, Paclobutrazol,Propiconazole, and 1,2,4-triazole were measured by LC/MS/MS using an ABSCIEX Triple Quad LC/MS/MS (obtained from the AB SCIEX Company ofFramingham, Mass.); the results are shown in FIG. 1 and listed in Table1.

TABLE 1 Increase in the measured amounts of pesticides or the metabolite1,2,4-triazole in supernatants collected from sand vs. the coated sandproduct of Example 5. Increase conc. measured in silica sand supernatantrelative to amount in Pesticide/Metabolite coated sand supernatant (%)1,2,4 Triazole 80 Azoxystrobin 827 Paclobutrazol 116 Propiconazole 664

Then 1 mL aliquots of each aqueous supernatant sample were removed andtreated to replace the water with acetone in order to analyze thesupernatant by GC/MS. First 1 mL acetone was added to each 1 mLsupernatant aliquot with mixing. The resultant solution was evaporatedunder a stream of Argon at ambient laboratory temperature for 2 hours.Then 1 mL of acetone was then added to each sample and the samples wereevaporated to dryness for about 4 hrs under a stream of Argon at ambientlaboratory temperature. Then the dried residue was dissolved in 1 mL ofacetone and analyzed via GC/MS using a Shimadzu 2010 GC/MS (obtainedfrom the Shimadzu Corporation of Nakagyo-ku, Kyoto, Japan); the resultsare shown in FIG. 2.

All vials were then decanted and were rinsed once with deionized H₂O.Each vial was then extracted twice with 10 ml acetone, then 15 mlacetone. The acetone extracts were combined and were dehydratedsimilarly to the supernatant aliquots above. Four mL were decanted foranalysis. Chlorothalonil, Azoxstrobin, Paclobutrazol, and Propiconazolewere measured by GC/MS using a Shimadzu 2010 GC/MS (obtained from theShimadzu Corporation of Nakagyo-ku, Kyoto, Japan); the results are shownin FIG. 3.

EXAMPLE 7

A 500 ml mason jar was charged with 110 g resorcinol (obtained from theIndspec Chemical Corporation of Petrolia, Pa.) and 80 g water, and thecontents of the jar were stirred and warmed until the resorcinol wasdissolved. Then 25 g of a 37 wt % aqueous solution of formaldehyde wasadded with vigorous stirring, followed by slow addition of 1.8 g conc.H₂SO₄. The resulting mixture was stirred at ambient laboratorytemperature for about 8 hours. Then the pH was adjusted to 5.8 using23.5 g of a 50% w/w KOH solution. The resultant resorcinol novalacproduct was found to be 57% solids.

Then 16 g of the resorcinol novalac product was removed from the jar andplaced in a fresh 500 ml mason jar equipped with a magnetic stir bar; 48g deionized H₂O was added to the jar and this mixture was stirred andsparged with Argon. Then 10.6 g of the 50% KOH solution was added to thejar with stirring. Then 100 g MPEG 5000 Br was added slowly to the jarover 30 minutes, accompanied by vigorous stirring. After the additionwas completed, stirring was continued for an additional 45 minutes. Then329 g CASCOPHEN® OS 707M (obtained from MOMENTIVE™ PerformanceMaterials, LLC of Columbus, Ohio) was added to the jar with vigorousstirring.

About 25 g of this mixture was removed from the flask and added to 900 gsilica sand in a Cleveland-type laboratory benchtop muller and thecombination was thoroughly mixed. Then 8 g CASCOPHEN® W3154N-1 (obtainedfrom MOMENTIVE™ Performance Materials), 0.3 g phthalocyanine blue and 3g BAYERFERROX® 91LO Yellow (obtained from Lanxess AG of Cologne,Germany) were added to the muller and this combination was mixed forabout 1 minute. Then 70 g of PANTHER CREEK® 200 Calcium Bentonite(obtained from the American Colloid Company of Hoffman Estates, IL) wasadded to the muller and this combination was mixed for about 1 minute toresult in a coated sand product. The coated sand product was removedfrom the muller and heated in an oven set at 150° C.; once the materialreached 130° C., heating was continued for about 10 minutes. Then thecoated sand products was allowed to cool to ambient laboratorytemperature. After cooling the pH of the coated sand was adjusted toabout 5.5 by spraying the sand with 15% sulfuric acid solution.

Upon microscopic examination, the coated sand product was observed topossess a uniform coating including resin, pigment and clay. When asample of the coated sand was added to water and shaken, the coating wasinsoluble, but easily wettable; and no foaming was observed. Two dropsof 0.5 wt % Methylene Blue dye in water was added to the coated sand inwater and the slurry was shaken briefly then allowed to stand forseveral minutes followed by decanting the water from the sand; the sandwas rinsed with clean water. The sand exhibited a purple sheen,characteristic of the association of the dye with the cation exchangesites of the clay.

Sorption and desorption of ammonium ions, and sorption and desorption ofselected pesticides on the composites surface were demonstrated usingthe techniques and materials of Examples 5 and 6. The results weresimilar to those observed for Examples 5 and 6.

EXAMPLE 8

A 500 ml mason jar was charged with 16.5 g CASCOPHEN® G 1149A (obtainedfrom MOMENTIVE™ Performance Materials, LLC of Columbus, Ohio) and 48 gdeionized H₂O and the mixture was sparged with Argon. Then 7.4 g 50% w/wNaOH was added with stirring. Then 100 g MPEG 5000 Br was added slowlyto the jar over 30 minutes, accompanied by vigorous stirring. After theaddition was completed, stirring was continued for an additional 45minutes. Then 329 g CASCOPHEN® OS 707M (obtained from MOMENTIVE™Performance Materials, LLC of Columbus, Ohio) was added to the jar withvigorous stirring.

About 25 g of this mixture was removed from the flask and added to 900 gsilica sand in a Cleveland-type laboratory benchtop muller and thecombination was thoroughly mixed. Then 8 g CASCOPHEN® W3154N-1 (obtainedfrom MOMENTIVE™ Performance Materials), 0.3 g phthalocyanine blue and 3g BAYERFERROX® 91LO Yellow (obtained from Lanxess AG of Cologne,Germany) were added to the muller and this combination was mixed forabout 1 minute. Then 70 g of PANTHER CREEK® 200 Calcium Bentonite(obtained from the American Colloid Company of Hoffman Estates, IL) wasadded to the muller and this combination was mixed for about 1 minute toresult in a coated sand product. The coated sand product was removedfrom the muller and heated in an oven set at 150° C.; once the materialreached 130° C., heating was continued for about 10 minutes. Then thecoated sand products was allowed to cool to ambient laboratorytemperature. After cooling the pH of the coated sand was adjusted toabout 5.5 by spraying the sand with 15% sulfuric acid solution.

Upon microscopic examination, the coated sand product was observed topossess a uniform coating including resin, pigment and clay. When asample of the coated sand was added to water and shaken, the coating wasinsoluble, but easily wettable; and no foaming was observed. Two dropsof 0.5 wt % Methylene Blue dye in water was added to the coated sand inwater and the slurry was shaken briefly then allowed to stand forseveral minutes followed by decanting the water from the sand; the sandwas rinsed with clean water. The sand exhibited a purple sheen,characteristic of the association of the dye with the cation exchangesites of the clay.

Sorption and desorption of ammonium ions, and sorption and desorption ofselected pesticides on the composites surface were demonstrated usingthe techniques and materials of Examples 5 and 6. The results weresimilar to those observed for Examples 5 and 6.

EXAMPLE 9

A 1 L mason jar was charged with 80 g of the resorcinol novalac productof Example 6 and 240 g deionized H₂O, and the mixture was sparged withArgon. Then 37 g of 50% w/w NaOH was added with stirring. Then 500 g ofMPEG 5000 Br was slowly added with stirring over 30 min, after which themixture was stirred for another hour. Then 10 g of a 37 wt % aqueousformaldehyde solution was added to the jar. The jar was placed on ahotplate/stirrer and maintained at 55° C. under Argon blanket for 2hours. After removing from the hotplate, 810 g of a gel-like materialwas recovered.

The gel was tested for formaldehyde using the PURPALD® test (reagentobtained from the Sigma-Aldrich Company of St. Louis, Mo. and usedaccording to the manufacturer's directions). No formaldehyde wasdetected.

Then 270 g of the gel and 600 g deionized H₂O were placed in a WARING®blender (obtained from the Conair Corp. of Stamford, Conn.) and theblender was turned to “HIGH” for 5 min. The resulting mixture was thenhomogenized using a rotor/stator type homogenizer. Then 6.4 g of a 69 wt% aqueous solution of (3-chloro-2-hydroxypropyl) trimethylammoniumchloride (Quat 188, obtained from the Dow Chemical Company of Midland,Mich.) was added to the homogenized mixture, and this mixture wasstirred overnight at 50° C. under Argon. An emulsified mixture resulted.The pH of the emulsion was adjusted to 6.0 with conc. sulfuric acid.

Adsorption of dyes by the Quat 188 gel was tested by adding 0.25 mL 0.1%bromophenol blue to a 20 mL ground gel aliquot, and adding 0.25 mL 0.1%bromothymol blue to a second 20 mL ground gel aliquot. The gel aliquotswere stirred for 30 minutes, then were centrifuged at 2000 rpm for 45min. along with water controls having the dyes dissolved therein. Theresulting supernatants from the two gel aliquots were colorless andwater clear. The water controls were blue.

The remainder of the gel was dried by spreading in a baking dish andplacing the dish in an oven set to 50° C. until dry. The dry product wascoarsely ground in a coffee grinder. The ground product was placed in aball mill and rotated for about 48 hours to obtain a powder. The powderwas used to coat pumpkin seeds, corn, and black beans using polyvinylalcohol (PVA; MOWIOL® 10-98, obtained from the Sigma-Aldrich Company ofSt. Louis, Mo.) as an adhesive. Several drops of a 10 wt % PVA solutionin water were placed on a glass plate, and the seeds were wetted with itand then allowed to stand at ambient laboratory temperature for about 30min or until they developed a tacky surface. The seeds were then rolledin the powder until well coated; then the coated seeds were allowed todry completely at ambient laboratory temperature. Uncoated seeds weregerminated side by side with those coated with the powder. No differencein germination or early growth between coated and uncoated seeds wereseen.

EXAMPLE 10

Unamended sphagnum peat moss was dried by placing it in an oven at 93°C. for 2 days. The dry peat exhibited strong hydrophobicity in that adrop of water placed upon the dried peat remained intact on the surface,and eventually evaporated over time without soaking into the mossfibers. Aliquots of the emulsion prepared in Example 9 corresponding to3 g, 4.5 g, 6.0 g, and 7.5 g of solids were added to the moss byadmixing each aliquot with 20 g of the moss. After the emulsion was dry,addition of a drop of water placed on the peat resulted in water droppenetration times of >10 min, >1 min, 1 min, and <10 sec respectively.No amount of additional drying of the peat sample containing 7.5 g ofemulsion solids could regenerate the hydrophobicity of the originalunamended and dried peat.

EXAMPLE 11

A 1 liter roundbottom flask was charged with 4.67 g of the resorcinolnovalac of Example 6 and 14 g deionized H₂O and the mixture was spargedwith Argon. Then 2.1 g of a 50% solution of NaOH was added withstirring. Then 29 g of MPEG 5000 Br was slowly added with stirring over30 minutes, then stirring was continued for an additional 1 hour. Then200 ml cyclohexane and 20 g Triton X-100 (obtained from the Dow ChemicalCompany of Midland, Mich.) were added to the flask. The mixture washeated to reflux temperature, and during vigorous agitation under refluxconditions 0.6 g of 37 wt % aqueous formaldehyde solution was added andthe temperature adjusted to maintain reflux. After two hours of stirringunder reflux conditions, 200 ml of deionized H₂O was added and thecyclohexane distilled from the flask. Upon cooling to ambienttemperature, the remaining mixture was a stable emulsion. The emulsionwas further reacted with (3-chloro-2-hydroxypropyl) trimethylammoniumchloride (Quat 188), followed by pH adjustment, as described in Example9.

EXAMPLE 12

A 1 liter mason jar was charged with of 80 g of the resorcinol novalacof Example 6 and 240 g deionized H₂O and the mixture was sparged withArgon. Then 37 g of a 50% solution of NaOH was added to the mixture withstirring. Then 500 g of MPEG 5000 Br was slowly added with stirring over30 min, and the mixture was allowed to stir for an addition 1 hour. Then10 g of a 37% solution of formaldehyde was added to the mixture. The jarwas placed on a hotplate/stirrer and maintained at 55C under Argonblanket, with stirring, for 2 hours. After cooling the mixture, 810 g ofa gel-like material was recovered.

The gel was tested for formaldehyde using the PURPALD® test (reagentobtained from the Sigma-Aldrich Company of St. Louis, Mo. and usedaccording to the manufacturer's directions). No formaldehyde wasdetected. Then 270 g of the gel and 600 g deionized H₂O were placed in aWARING® blender (obtained from the Conair Corp. of Stamford, Conn.) andthe blender was turned to “HIGH” for 5 min. The resulting mixture wasthen homogenized using a rotor/stator type homogenizer. Then 3 gformaldehyde and 3 g sodium sulfite were added to the homogenizedmixture and the resulting mixture was sparged with Ar and warmed withagitation at 50° C. for 6 hours, followed by adjustment of the pH to6.0. A stable emulsion was observed.

The emulsion adsorbed the cationic dye Methylene Blue and upon mixingwas observed to have the characteristic purple color indicative of theoccupation of the anionic SO3²⁻ exchange sites by the dye.

CONTROL EXAMPLE A

A 250 Erlenmeyer flask was charged with 33.01 g 90% phenol, 38.78 g 37%formaldehyde, 1.2 g ZnO, and 1.8 g glacial acetic acid; these amountscorrespond to a mole ratio of 1:1.5 phenol:formaldehyde. Then the flaskwas equipped with a condenser and placed on a hotplate stirrer andheated to reflux. The contents of the flask were refluxed for about 2hours. Then the condenser was removed; a strong odor of formaldehyde andphenol was evident, and the viscosity of the flask had not appeared toincrease noticeably. The pH of the contents was measured and was foundto be 4.75. Then 75.5 g MPEG 750 (obtained from the Sigma-AldrichCompany of St. Louis, Mo.) was added to the flask and the flask washeated to 95-100° C. under simple distillation conditions for about 3.5hours. No noticeable increase in viscosity was observed during thistime; the contents of the flask were amber colored. About 24 mL of adistillate was recovered.

¹³C NMR (DMSO) was carried out on the contents of the flask, and ¹³C NMR(DMSO) was also carried out for MPEG 750 alone. These ¹³C NMR traces areshown in FIG. 4 as trace A (MPEG 750 alone), and trace B (contents ofthe flask). The ¹³C NMR peak area was determined for peak regionscorresponding to MPEG backbone carbons present in trace A at 70-71 ppmand the terminal MPEG carbon adjacent to the hydroxyl moiety present intrace A at 60.5-62 ppm. Then a ratio, Q, was determined as the ratio ofbackbone carbons to terminal hydroxylated carbons based on these twoarea calculations. Ratio Q_(A), the ratio of backbone carbon to terminalhydroxylated carbon for MPEG detected n trace A, was calculated to be28.54. The ratio Q_(B) was calculated as the ratio of MPEG backbonecarbon to terminal hydroxylated carbon for MPEG detected in trace B.Q_(B) was calculated to be 27.94.

FIG. 5 shows a theoretical ¹³C NMR trace of the indicated benzyl MPEGether structure shown, as scan E. The theoretical peaks were generatedby MNova 8.1.2 NMR Software with Modgraph NMR prediction add-on(obtained from Mestrelab Research, Santiago, Spain). The theoreticaltrace is overlaid on the actual ¹³C NMR trace of the contents of theflask, as trace F. In trace F, the absorption corresponding to theterminal hydroxylated carbon is labeled. Also labeled in trace F areabsorptions attributed to aromatic methylol ether carbons present in theortho/para (o/p) configuration vs. ortho/ortho (o/o) configuration,clearly showing that both configurations arise as a result of thereaction.

Additionally, the ¹³C NMR trace of the contents of the flask showednumerous absorbances characteristic of unreacted phenol in the region ofabout 115 ppm to 160 ppm (not shown). Based on phenol resonances in thearomatic region, it was estimated that about 24.5% phenol moieties inthe flask were unreacted.

CONTROL EXAMPLE B

A 250 Erlenmeyer flask was charged with 79.7 g (90%) phenol, 18.8 gparaformaldehyde, 0.7 g water and 0.8 g calcium acetate, and the flaskwas equipped with a condenser and a stir bar. These amounts correspondto a mole ratio of 1:0.82 phenol:formaldehyde. The flask was placed on ahotplate stirrer and slowly heated to reflux over a period of about 1hour while stirring. Reflux was continued for an additional hour atwhich point heat was removed and 98 g of product recovered.

Then the product was split by adding 48 g of product into each of two125 ml Erlenmeyer flasks. To one of the flasks was added 4.8 g MPEG 750(obtained from the Sigma-Aldrich Company of St. Louis, Mo.). Both flaskswere equipped with condensers and refluxed for about 2 hours. Theviscosity was observed to increase substantially in both flasks. Uponcooling, both appeared as extremely viscous white products, estimated tobe at least about 20 poise. The flask containing the MPEG had a minoramount of a second clear phase.

¹³C NMR (DMSO) was carried out on the contents of both flasks. These ¹³CNMR scans are shown in FIG. 4 as scan C (no MPEG) and scan D (MPEGadded). The Q ratio for scan D, Q_(D), was calculated to be 24.94 usingthe MPEG peaks indicated in Control Example A for MPEG detected in thescan.

FIG. 6 shows the theoretical ¹³C NMR trace of the indicated benzyl MPEGether structure shown, as scan E (same theoretical trace as shown inFIG. 5). The theoretical trace is overlaid on the actual ¹³C NMR traceof the contents of the flask containing MPEG, as trace G, and thecontents of the flask without MPEG, as trace H. In trace G, theabsorption corresponding to the terminal hydroxylated carbon of MPEG islabeled. Labeled in trace H are absorptions attributed to phenol-phenolmethylol ether carbons present in the ortho/para (o/p) configuration vs.ortho/ortho (o/o) configuration, clearly showing that o/p configurationdominates the condensation in this case; these peaks are present intrace G as well and appear to be approximately the same relative size asthose in trace H.

Additionally, the ¹³C NMR trace of the contents of the flask withoutMPEG showed numerous absorbances characteristic of unreacted phenol inthe region of about 115 ppm to 160 ppm (not shown). Based on phenolresonances in the aromatic region, it was estimated that about 36.1%phenol moieties in the flask were unreacted.

EXAMPLE 13

A 250 mL reaction vessel was charged with 75 g MPEG 750 and 3.4 ml PBr₃.The contents of the vessel were stirred under Argon blanket and heatedto 70° C., and maintained at 70° C. with stirring for about 3.5 hours.The product of the reaction is referred to below as “MPEG 750-Br”.

Then a second vessel was charged with 110 g resorcinol and 65 ml ofwater; this mixture was warmed with agitation until all solids weredissolved. Then 25 g of 37% formaldehyde was added to the flask withstirring. Then 1 ml conc H₂SO₄ was added slowly to the flask. Thecontents of the flask were heated to 60° C. with stirring for about 2hours. Then the pH of the contents was adjusted to 5.5 with a 50% KOHsolution. The final product was an R/F novalac (resorcinol/formaldehydenovalac) The product (solution) was weighed and the weight expressed asa percent of the starting weight of the resorcinol to yield a 56% R/Fnovalac. The novalac was analyzed by ¹³C NMR. The ¹³C NMR trace is shownin FIG. 7, as trace J.

A third vessel was charged with 19.67 g of the R/F(resorcinol/formaldehyde) novalac (0.1 mole resorcinol), 15 mL water,and 11 mL of a 50% KOH solution. The contents of the vessel were stirredto form a homogeneous mixture and blanketed with Argon. Then theentirety of the MPEG 750-Br was added in approximately 10 mL portionswith vigorous stirring over a period of about 30 minutes. After theaddition was complete, the mixture was heated to 50° C. with stirringfor about 2 hours. Then the pH of the mixture was adjusted to 7.5 withconc. H₂SO₄. Then the contents of the flask were centrifuged and thesupernatant collected and analyzed by ¹³C NMR. The ¹³C NMR trace isshown in FIG. 7, as trace K.

Comparison of traces J and K in FIG. 7 reveals the formation of anaromatic ether product of resorcinol and MPEG, as indicated by the peakobserved at about 160.3 ppm. This peak is associated with the aromaticether of PEG, specifically the aromatic ring carbon bonded to the etheroxygen, as determined by a theoretical absorption generated by MNova8.1.2 NMR Software with Modgraph NMR prediction add-on (obtained fromMestrelab Research, Santiago, Spain).

EXAMPLE 14

In a first vessel, MPEG 750-Br was synthesized using the procedure ofExample 13. In a second vessel, an R/F novalac having 56% resorcinol w/wwas synthesized using the procedure of Example 13.

Then a third vessel was charged with 19.67 g of the R/F novalac (0.1mole resorcinol), 11 mL 50% KOH solution, and 50 mLdimethoxypolyethylene glycol 500 (obtained from the Sigma-AldrichCompany of St. Louis, Mo.) with stirring and under Argon blanket. Themixture was heated to boiling, and a liquid was observed to distil at110° C. Distillation was continued for about 2 hours, until distillationceased. Then MPEG 750-Br was then added to the vessel in 10 cc portionsover a period of about 0.5 hour with vigorous stirring until theentirety of the product formed above was added. The contents of thevessel were maintained at 50° C. with stirring for about 2 hours. Aftercooling, the pH of the contents of the vessel were adjusted to 7.5 withconc. H₂SO₄. The product was centrifuged to remove inorganic salts.

G. Representative Embodiments

While the invention is susceptible to various modifications andalternative forms, specifics thereof have been shown by way of examples,and are described in detail. It should be understood, however, that theinvention is not limited to the particular embodiments described. On thecontrary, the intention is to cover modifications, equivalents, andalternatives falling within the spirit and scope of the invention. Invarious embodiments, the invention suitably comprises, consistsessentially of, or consists of the elements described herein and claimedaccording to the claims.

Additionally each and every embodiment of the invention, as describedhere, is intended to be used either alone or in combination with anyother embodiment described herein as well as modifications, equivalents,and alternatives thereof falling within the spirit and scope of theinvention. Representative but non-limiting embodiments and combinationsthereof include the following.

A first embodiment of the invention is an ether adduct having thestructure X—O—Y, wherein X is the residue of a polyhydroxylated aromaticcompound, O is oxygen, and Y is a group comprising at least 10polyalkylene oxide repeat units. In some such embodiments, X is theresidue of resorcinol or a resorcinol oligomer with formaldehyde. Insome such embodiments, Y is the residue of a linear polyethylene oxide;in some such embodiments the polyethylene oxide includes between 50 and200 ethylene oxide repeat units; in some such embodiments, thepolyethylene oxide comprises a methyl ether endgroup.

A second embodiment is a composition comprising the reaction product ofan ether adduct and a phenolic aldehyde prepolymer, or an aldehyde, or acombination thereof, the ether adduct having the structure X—O—Y,wherein X is the residue of a polyhydroxylated aromatic compound, O isoxygen, and Y is a group comprising at least 10 polyalkylene oxiderepeat units. In some such embodiments, Y is the residue of a linearpolyethylene oxide having between 50 and 200 ethylene oxide repeat unitsand a methyl ether endgroup. In some such embodiments, X is the residueof resorcinol or a resorcinol oligomer with formaldehyde. In some suchembodiments, the phenolic aldehyde prepolymer is a resole. In some suchembodiments, the reaction product consists essentially of an etheradduct and an aldehyde; in some such embodiments, the reaction productis divided. In some such embodiments, the composition further comprisesa fertilizer, a pesticide, an herbicide, a nematicide, two or morethereof, or a combination thereof.

A third embodiment is an article comprising particles and a compositioncomprising the reaction product of an ether adduct and a phenolicaldehyde prepolymer, or an aldehyde, or a combination thereof, the etheradduct having the structure X—O—Y, wherein X is the residue of apolyhydroxylated aromatic compound, O is oxygen, and Y is a groupcomprising at least 10 polyalkylene oxide repeat units. In someembodiments, the composition is coated on the surface of the particles.In some embodiments, the composition is present at a coating weight ofabout 0.1 to 25 wt % based on the weight of the uncoated particles. Insome embodiments, the particle is sand. In some embodiments, theparticle is clay. In some embodiments, the article further comprises acombination of particles. In some embodiments, the particles aremicroparticles or nanoparticles. In some embodiments, the articlefurther comprises a fertilizer, a pesticide, an herbicide, a nematicide,two or more thereof, a mixture thereof, or a combination thereof.

A fourth embodiment is a reactive composition comprising an ether adducthaving the structure X—O—Y, wherein X is the residue of apolyhydroxylated aromatic compound, O is oxygen, and Y is a groupcomprising at least 10 polyalkylene oxide repeat units; a phenolicaldehyde prepolymer, an aldehyde, or a combination thereof; and a curecatalyst. In some such embodiments, the reactive composition is coatedon a substrate. In some such embodiments, the substrate is a particle;in some such embodiments, the particle includes sand, clay, or acombination thereof.

A fifth embodiment is a method of forming a cured composition, themethod comprising: reacting a polyhydroxylated aromatic compound with apolyalkylene oxide comprising at least an hydroxyl group and 10polyalkylene oxide repeat units to form an ether adduct thereof;combining the ether adduct with a phenolic aldehyde prepolymer, analdehyde, or a combination thereof, and a cure catalyst to form areactive composition; and reacting the reactive composition to form acured composition. In some such embodiments, the reactive composition iscoated on a substrate. In some such embodiments, the ether adduct isstored for a period of time prior to forming a reactive composition,wherein the period of time is up to a month, or up to a year, or longerthan a year.

I claim:
 1. A composition comprising the reaction product of a. an etheradduct and b. a phenolic aldehyde prepolymer, an aldehyde, or acombination thereof, the ether adduct having the structure X—O—Y,wherein X is the residue of a polyhydroxylated aromatic compound free ofmethylol moieties, O is oxygen, and Y is a group comprising from about10 to 1000 polyalkylene oxide repeat units. polyalkylene oxide repeatunits.
 2. The composition of claim 1 wherein Y is the residue of alinear polyethylene oxide, a linear polypropylene oxide, a mixturethereof, or a random or block copolymer thereof.
 3. The composition ofclaim 1 wherein Y is the residue of a linear polyethylene oxide havingbetween 50 and 200 ethylene oxide repeat units and a methyl etherendgroup.
 4. The composition of claim 1 wherein X is the residue ofresorcinol or a resorcinol oligomer with formaldehyde.
 5. Thecomposition of claim 1 wherein the ratio of ether adduct to phenolicaldehyde prepolymer is between about 5:1 to 1:10 by weight.
 6. Thecomposition of claim 1 wherein the phenolic aldehyde prepolymer is aresole.
 7. The composition of claim 1 wherein the phenolic aldehydeprepolymer comprises a condensation product of resorcinol, phenol, or amixture thereof with formaldehyde.
 8. The composition of claim 1 whereinthe reaction product consists essentially of an ether adduct and analdehyde.
 9. The composition of claim 8, wherein the reaction product isa gel cured composition, and wherein the composition is mechanicallydisrupted.
 10. The composition of claim 1 further comprising afertilizer, a pesticide, an herbicide, a nematicide, two or morethereof, or a combination thereof.
 11. The composition of claim 1further comprising a reactive compound.
 12. An article comprising thecomposition of claim 1 disposed on the surface of sand particles. 13.The article of claim 12 wherein the composition of claim 1 is present ata coating weight of about 0.1 to 25 wt% based on the weight of theuncoated sand particles.
 14. The coated article of claim 12 furthercomprising a clay.
 15. The article of claim 12 further comprising afertilizer, a pesticide, an herbicide, a nematicide, two or morethereof, a mixture thereof, or a combination thereof.
 16. A reactivecomposition comprising a. an ether adduct; b. a phenolic aldehydeprepolymer, an aldehyde, or a combination thereof; and c. a curecatalyst, the ether adduct having the structure X—O—Y, wherein X is theresidue of a polyhydroxylated aromatic compound free of methylolmoieties, O is oxygen, and Y is a group comprising from about 10 to 1000polyalkylene oxide repeat units.
 17. The reactive composition of claim16 wherein the reactive composition is coated on a substrate.
 18. Acompound having the structure X—O—Y, wherein X is the residue of apolyhydroxylated aromatic compound free of methylol moieties, O isoxygen, and Y is a group comprising from about 10 to 1000 polyalkyleneoxide repeat units.
 19. The compound of claim 18 wherein X is theresidue of resorcinol or a resorcinol oligomer with formaldehyde. 20.The compound of claim 18 wherein Y is the residue of a linearpolyethylene oxide having between 50 and 200 ethylene oxide repeat unitsand a methyl ether endgroup.